KR101658675B1 - Positive resist composition, method of forming resist pattern, and polymeric compound - Google Patents

Abstract

A positive resist composition comprising a base component (A) that increases solubility in an alkali developing solution by the action of an acid and an acid generator component (B) that generates an acid upon exposure, wherein the base component (A) (A1) having a structural unit (a0) represented by the following general formula (a0-1) and a structural unit (a1) derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group, Resist composition.
[Chemical Formula 1]

Description

TECHNICAL FIELD [0001] The present invention relates to a positive resist composition, a resist pattern forming method, and a polymeric compound (a positive resist composition, a method of forming a resist pattern, and a polymeric composition)

The present invention relates to a positive resist composition, a resist pattern forming method using the positive resist composition, and a polymer compound useful as a positive resist composition.

The present application claims priority based on Japanese Patent Application No. 2009-248210 filed on October 28, 2009, the contents of which are incorporated herein by reference.

In the lithography technique, for example, a resist film made of a resist material is formed on a substrate, selective exposure is performed with radiation such as light or electron beams through a mask having a predetermined pattern formed thereon, Thereby forming a resist pattern of a predetermined shape on the resist film.

A resist material in which the exposed portion is changed to a property dissolving in the developing solution is referred to as a positive type and a resist material in which the exposed portion is changed into a property not dissolved in the developing solution is referred to as a negative type.

BACKGROUND ART [0002] In recent years, in the production of semiconductor devices and liquid crystal display devices, miniaturization of patterns has progressed rapidly according to the progress of lithography technology. In the refinement method, generally, the exposure light source is made shorter in wavelength (higher energy). Specifically, conventionally, ultraviolet rays represented by g-line and i-line have been used, and now, mass production of semiconductor devices using a KrF excimer laser or an ArF excimer laser has been started. EB (electron beam), EUV (extreme ultraviolet ray), X-ray and the like having a shorter wavelength (high energy) than these excimer lasers have also been studied.

In accordance with the shortening of the wavelength of the exposure light source, the resist material is required to have improved lithography properties such as sensitivity to an exposure light source and resolution capable of reproducing a pattern of minute dimensions. A chemically amplified resist is known as a resist material that satisfies these requirements. As the chemically amplified resist, a composition containing a base component whose solubility in an alkaline developer is changed by the action of an acid and an acid generator component which generates an acid by exposure is generally used. For example, in the case of a positive-type chemically amplified resist composition, as the base component, the solubility of the base component in an alkaline developer is increased by the action of an acid.

Conventionally, a resin (base resin) is mainly used as a base component of a chemically amplified resist composition. In the case of the positive type, as the base resin, a resin which increases the solubility in an alkali developing solution by the action of an acid is generally used.

As the base resin of the chemically amplified resist composition used in the ArF excimer laser lithography at present, it is preferable that a base resin having a structural unit derived from a (meth) acrylate ester in the main chain is used because it has excellent transparency at around 193 nm Resin (acrylic resin) is used (see, for example, Patent Document 1). Here, "(meth) acrylic acid" means one or both of acrylic acid having a hydrogen atom bonded to the? -Position and methacrylic acid having a methyl group bonded to the? -Position. "(Meth) acrylic acid ester" means one or both of an acrylate ester having a hydrogen atom bonded to the α-position and a methacrylate ester having a methyl group bonded to the α-position. The term "(meth) acrylate" means one or both of an acrylate having a hydrogen atom bonded to the α-position and a methacrylate having a methyl group bonded to the α-position.

Further, in addition to the base resin and the acid generator, a nitrogen-containing organic compound such as an alkylamine, an alkyl alcohol amine or the like is currently mixed with a chemically amplified resist (see, for example, Patent Documents 2 to 3). The nitrogen-containing organic compound acts as a quencher for trapping an acid generated from an acid generator, and contributes to improvement of lithography characteristics such as resist pattern shape and the like.

Japanese Patent Application Laid-Open No. 2003-241385 Japanese Patent Application Laid-Open No. 5-249662 Japanese Unexamined Patent Publication No. 5-232706 Japanese Patent Application Laid-Open No. 11-084660

In the future, there is a demand for new materials that can be used in lithography applications, while further advances in lithography technology and expansion of application fields are expected. For example, as the pattern is miniaturized, the resist material has not only resolution but also other exposure latitude (EL), mask error factor (MEEF), in-plane uniformity of pattern dimensions (critical dimensionality unity (CDU)) , And various improvements in lithography properties are required. In order to improve the yield, it is also important to reduce defects in the resist pattern formation.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a positive resist composition and a resist pattern forming method excellent in lithography characteristics and defective reduction effects, and a polymer compound useful for the positive resist composition.

The first aspect of the present invention which solves the above problems is characterized by comprising a base component (A) in which solubility in an alkali developer is enhanced by the action of an acid, and an acid generator component (B) As a positive resist composition,

(A) comprises a structural unit (a0) represented by the following general formula (a0-1) and a polymer (A1) having a structural unit (a1) derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group: Wherein the resist composition is a positive resist composition.

[Chemical Formula 1]

Wherein R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms; R ² and R ³ each independently represent a hydrogen atom or an alkyl group which may contain an oxygen atom at an arbitrary position, or both form an alkylene group; W represents a cyclic alkylene group which may contain an oxygen atom at an arbitrary position]

A second aspect of the present invention is a process for producing a resist pattern, comprising the steps of forming a resist film on a support using the positive resist composition of the first aspect, exposing the resist film, and forming a resist pattern by alkali development of the resist film And a resist pattern forming method.

A third aspect of the present invention is a polymer compound having a structural unit (a0) represented by the following general formula (a0-1) and a structural unit (a1) derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group.

(2)

Wherein R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms; R ² and R ³ each independently represent a hydrogen atom or an alkyl group which may contain an oxygen atom at an arbitrary position, or both form an alkylene group; W represents a cyclic alkylene group which may contain an oxygen atom at an arbitrary position]

In the present specification and claims, the term " aliphatic " is defined as meaning a group, compound, or the like having no aromaticity as a relative concept to an aromatic.

The "alkyl group" is intended to include linear, branched, and cyclic monovalent saturated hydrocarbon groups, unless otherwise specified. The alkyl group in the alkoxy group is also the same.

The "alkylene group" is intended to include linear, branched, and cyclic divalent saturated hydrocarbon groups unless otherwise specified.

The "halogenated alkyl group" is a group in which some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms, and the "halogenated alkylene group" is a group in which a part or all of the hydrogen atoms of the alkylene group are substituted with halogen atoms, An atom, a chlorine atom, a bromine atom, and an iodine atom.

The "hydroxyalkyl group" is a group in which a part or all of the hydrogen atoms of the alkyl group are substituted with hydroxyl groups.

"Constituent unit" means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).

&Quot; Exposure " is a concept including the entire irradiation of radiation.

According to the present invention, it is possible to provide a positive resist composition and a resist pattern forming method excellent in lithography characteristics and defects reduction effect, and a polymer compound useful for the positive resist composition.

≪ Positive Resist Composition >

The positive resist composition of the present invention comprises a base component (A) (hereinafter referred to as component (A)) in which solubility in an alkaline developer is enhanced by the action of an acid, and an acid generator Component (B) (hereinafter referred to as component (B)).

In such a positive resist composition, when the radiation is irradiated (exposed), an acid is generated from the component (B), and the solubility of the component (A) in the alkali developer is increased by the action of the acid. Therefore, in the formation of the resist pattern, when the resist film obtained using the positive resist composition is selectively exposed, the solubility of the exposed portion of the resist film in the alkali developing solution is increased, while in the alkali developing solution of the unexposed portion , The resist pattern can be formed by carrying out the alkali development.

Here, the "base component" means an organic compound having film-forming ability.

As the base component, an organic compound having a molecular weight of 500 or more is generally used. With a molecular weight of 500 or more, it is easy to form a nano-level resist pattern while having sufficient film forming ability.

An " organic compound having a molecular weight of 500 or more " is largely classified into a non-polymer and a non-polymer.

As the non-polymeric polymer, those having a molecular weight of usually 500 or more and less than 4000 are used. Hereinafter, the term " low molecular weight compound " refers to a non-polymeric substance having a molecular weight of 500 or more and less than 4000.

As the polymer, those having a molecular weight of 1000 or more are usually used. In the present specification and claims, " polymer compound " refers to a polymer having a molecular weight of 1000 or more.

In the case of the polymer compound, the " molecular weight " is defined as the weight average molecular weight in terms of polystyrene calculated by gel permeation chromatography (GPC).

≪ Component (A) > [Polymer compound (A1)] &

The polymeric compound (A1) (hereinafter referred to as the component (A1)) is obtained by copolymerizing the structural unit (a0) represented by the general formula (a0-1) and the structural unit (a1) derived from an acrylate ester containing an acid- Respectively.

The component (A1) may further contain, in addition to the structural units (a0) and (a1), a structural unit derived from an acrylate ester containing a -SO ₂ -containing cyclic group and a structural unit derived from an acrylate ester containing a lactone- And at least one structural unit (a2) selected from the group consisting of structural units.

The component (A1) may further comprise, in addition to the structural units (a0) and (a1), a structural unit derived from an acrylate ester containing a polar group-containing aliphatic hydrocarbon group in addition to the structural units (a0), (a1) And may have a unit (a3).

(A0), (a1) and (a3), in addition to the structural units (a0) and (a1) In addition, in addition to the structural units (a0), (a1), (a2) and (a3), a structural unit (a4) derived from an acrylic acid ester containing an aliphatic cyclic group further having acidity may be present.

(Constituent unit (a0))

The structural unit (a0) is represented by the general formula (a0-1).

In the formula (a0-1), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms.

The alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, -Butyl group, pentyl group, isopentyl group, neopentyl group and the like.

The fluorinated alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched fluorinated alkyl group, and examples thereof include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoro A perfluoroalkyl group, an ethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a perfluoroisobutyl group, a perfluoro-tert-butyl group, a perfluoropentyl group, And perfluoronopentyl group.

R is preferably a hydrogen atom, a methyl group or a trifluoromethyl group in view of industrial availability, more preferably a hydrogen atom or a methyl group.

In formula (a0-1), R ² and R ³ each independently represent a hydrogen atom or an alkyl group which may contain an oxygen atom at an arbitrary position, or both form an alkylene group.

The alkyl group for R ² and R ³ may be any of a linear chain, a branched chain and a cyclic group.

The linear or branched alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i- Butyl group, 2-methyl-2-butyl group, 3-methyl-2-butyl group, 1-pentyl group, 2-pentyl group and 3-pentyl group.

Examples of the cyclic alkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, 1-methyl-1-cyclopentyl group, 1-ethyl-1-cyclopentyl group, cyclohexyl group, Cyclohexyl group, 1-ethyl-1-cyclohexyl group, 1-methyl-1-cycloheptyl group, 1-ethyl-1-cycloheptyl group, 2-adamantyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, And the like.

When the alkyl group in R ² and R ³ is linear or branched, the alkyl group may have a cyclic alkyl group as a substituent.

When the alkyl group in R ² and R ³ is cyclic, the alkyl group may be substituted with a linear or branched alkyl group, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, an oxygen atom (= O ), And the like.

Each of the alkyl groups in R ² and R ³ may contain an oxygen atom at an arbitrary position. The fact that the alkyl group contains an oxygen atom means that an oxygen atom (-O-) is introduced into the carbon chain of the alkyl group. Examples of the alkyl group containing an oxygen atom include an acetal-type acid dissociable dissolution inhibiting group such as an alkoxyalkyl group described later.

When at least one of R ² and R ³ is an alkyl group which may contain an oxygen atom at an arbitrary position, the alkyl group may be an acid-dissociable group. That is, it may be a structural unit represented by the following general formula (a0-1-4).

(3)

[Formula (a0-1-4) of, R, R ^2, W are each as defined above formula (a0-1) in the R, R ^2, and W, Z ¹ is an acid-cleavable group;

The term "acid-dissociable group" means a group having properties (acid dissociability) that can be dissociated by the action of an acid generated from the component (B) upon exposure to light when a resist pattern is formed as a resist composition.

In such a constitutional unit, when an acid generated from the component (B) acts upon exposure by forming a resist pattern as a resist composition, the nitrogen atom at the terminal of the sulfamoyloxy group (OSO ₂ N group) and the acid dissociable group Lt; / RTI >

The acid-cleavable group in the structural unit (a0) is not particularly limited as long as it corresponds to an alkyl group which may contain an oxygen atom at an arbitrary position. For example, And can be appropriately selected from among those proposed. As such an acid-cleavable group, acetal-type acid-cleavable groups such as tertiary alkyl groups and alkoxyalkyl groups are widely known.

Examples of the acid-dissociable group as the tertiary alkyl group include the same as the tertiary alkyl ester-type acid dissociable, dissolution inhibiting groups exemplified in the following structural unit (a1).

Examples of the acetal-type acid-decomposable group include the acetal-type acid-dissociable, dissolution inhibiting groups exemplified in the following structural unit (a1).

When both of R ² and R ³ are bonded to form an alkylene group, the alkylene group is preferably a linear or branched alkylene group, more preferably a linear alkylene group. The alkylene group preferably has 1 to 5 carbon atoms, and examples thereof include an ethanediyl group, a propane-1,3-diyl group, and a butane-1,4-diyl group.

In the present invention, at least one of R ² and R ³ is preferably a hydrogen atom, and both of R ² and R ³ are hydrogen atoms, or R ² and R ³ Is an hydrogen atom and the other is an alkyl group which may contain an oxygen atom at an arbitrary position, and it is most preferable that both of R ² and R ³ are hydrogen atoms.

In formula (a0-1), W represents a cyclic alkylene group which may contain an oxygen atom at an arbitrary position.

The alkylene group preferably has 3 to 20 carbon atoms, more preferably 5 to 12 carbon atoms.

The alkylene group is preferably both monocyclic and polycyclic in that it has excellent various lithography properties. It is preferably a polycyclic type in that the lithography characteristics are improved by increasing the Tg and the etching resistance is further improved, and it is preferably 2 to 4 ring types.

Specific examples of the alkylene group include a cyclopropane-diyl group, a cyclobuta-1,2-diyl group, a cyclobuta-1,3-diyl group, a cyclopenta-1,2-diyl group, , A cyclohexa-1,2-diyl group, a cyclohexa-1,3-diyl group, a cyclohexa-1,4-diyl group, a bicyclo [2.2.1] hepta- Hept-2,5-diyl group, bicyclo [2.2.1] hept-2,5-diyl group, 7-oxabicyclo [2.2.1] hept- Diyl group, 7-oxabicyclo [2.2.1] hepta-2,6-diyl group, adamantan-1,3-diyl group, and adamantan-1,2-diyl group.

More specific examples of the structural unit (a0) include structural units represented by the following formulas (a0-1-10) to (a0-1-72).

In the following formulas, Me represents a methyl group.

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

In the component (A1), one kind of the structural unit (a0) may be used alone, or two or more kinds may be used in combination.

The proportion of the constituent unit (a0) in the component (A1) is preferably 1 to 40 mol%, more preferably 1 to 35 mol%, and still more preferably 5 to 30 mol% based on the total constituent units constituting the component (A1) , And particularly preferably from 5 to 25 mol%. The lithographic properties such as EL, MEEF, CDU and the like are improved by setting it to the lower limit value or less, and when it is not more than the upper limit value, balance with other constituent units can be obtained.

(Constituent unit (a1))

The structural unit (a1) is a structural unit derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group. Also, even in the case of "a structural unit derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group", the structural unit corresponding to the structural unit represented by the general formula (a0-1) corresponds to the structural unit (a0) a1).

Herein, in the present specification and claims, "structural unit derived from an acrylate ester" means a structural unit composed of an ethylenic double bond of an acrylate ester cleaved.

The term " acrylic acid ester " includes not only an acrylate ester in which a hydrogen atom is bonded to a carbon atom at an alpha position, but also a substituent group (atom or group other than hydrogen atom) bonded to a carbon atom at the alpha position. Examples of the substituent bonded to the carbon atom at the? -Position include an alkyl group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, and a hydroxyalkyl group. The carbon atom at the? -Position of the acrylate ester refers to a carbon atom to which a carbonyl group is bonded, unless otherwise specified.

Specific examples of the alkyl group having 1 to 5 carbon atoms as a substituent at the α-position in the acrylate ester include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, And linear or branched alkyl groups having 1 to 5 carbon atoms such as a pentyl group and a neopentyl group.

Specific examples of the halogenated alkyl group having 1 to 5 carbon atoms as a substituent at the? -position include groups in which a part or all of the hydrogen atoms of the "alkyl group having 1 to 5 carbon atoms as a substituent at the? -position" are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.

The alkyl group of 1 to 5 carbon atoms or the halogenated alkyl group of 1 to 5 carbon atoms is preferably bonded to the α-position of the acrylate ester, and a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, or a fluorinated alkyl group of 1 to 5 carbon atoms More preferably a hydrogen atom or a methyl group in view of industrial availability.

The " acid dissociable dissolution inhibiting group " refers to an alkali dissolution inhibiting group which causes all the component (A1) to be resistant to alkali developing solution before dissociation, and an acid dissociable property which can be dissociated by the action of an acid generated from the component Lt; / RTI > When the acid dissociable dissolution inhibiting group in the constituent unit (a1) is dissociated, the solubility of the entire component (A1) in an alkaline developer is increased.

As the acid dissociable dissolution inhibiting group in the constituent unit (a1), those proposed as the acid dissociable dissolution inhibiting groups of the base resin for chemically amplified resists can be used. Generally, a group which forms a cyclic or chain type tertiary alkyl ester with a carboxyl group in (meth) acrylic acid or the like; An acetal type acid dissociable, dissolution inhibiting group such as an alkoxyalkyl group and the like are widely known. The term "(meth) acrylic acid ester" means one or both of an acrylate ester having a hydrogen atom bonded to the α-position and a methacrylate ester having a methyl group bonded to the α-position.

The term "tertiary alkyl ester" as used herein means an ester in which the hydrogen atom of the carboxyl group is substituted with a chain or cyclic alkyl group, and the terminal oxygen of the carbonyloxy group (-C (O) -O-) Represents a structure in which a tertiary carbon atom of the chain type or cyclic alkyl group is bonded to an atom. In this tertiary alkyl ester, when an acid acts, the bond between the oxygen atom and the tertiary carbon atom is cleaved.

The chain or cyclic alkyl group may have a substituent.

Hereinafter, the group which is acid-labile by constituting the carboxyl group and the tertiary alkyl ester is referred to as " tertiary alkyl ester-type acid dissociable, dissolution inhibiting group "

Examples of the tertiary alkyl ester-type acid dissociable, dissolution inhibiting group include an aliphatic branched-chain acid dissociable dissolution inhibiting group and an acid dissociable dissolution inhibiting group containing an aliphatic cyclic group.

Here, the term " aliphatic branched chain type " refers to a branched chain type structure having no aromaticity. The structure of the " aliphatic branched-chain acid dissociable, dissolution inhibiting group " is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but is preferably a hydrocarbon group. The "hydrocarbon group" may be either saturated or unsaturated, but is preferably saturated.

Examples of the aliphatic branched-chain acid dissociable, dissolution inhibiting groups include groups represented by -C (R ⁷¹ ) (R ⁷² ) (R ⁷³ ). In the formula, R ⁷¹ to R ⁷³ are each independently a linear alkyl group having 1 to 5 carbon atoms. The group represented by -C ( ^R71 ) ( ^R72 ) ( ^R73 ) preferably has 4 to 8 carbon atoms, and specific examples thereof include a tert-butyl group, a 2-methyl- Pentyl group, 3-methyl-3-pentyl group and the like. A tert-butyl group is particularly preferred.

The "aliphatic cyclic group" means a monocyclic or polycyclic group having no aromaticity.

The aliphatic cyclic group in the " acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group " may or may not have a substituent group. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).

The structure of the basic ring excluding the substituent of the aliphatic cyclic group is not limited to a group consisting of carbon and hydrogen (hydrocarbon group), but is preferably a hydrocarbon group. In addition, the hydrocarbon group may be either saturated or unsaturated, but is preferably saturated.

The aliphatic cyclic group may be monocyclic or polycyclic.

Examples of the aliphatic cyclic group include groups in which one or more hydrogen atoms have been removed from a monocycloalkane which may be substituted with an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a fluorinated alkyl group, which may be unsubstituted, a bicycloalkane, And groups obtained by removing one or more hydrogen atoms from polycycloalkane such as tricycloalkane, tetracycloalkane, and the like. More specifically, there may be mentioned a group in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane or cyclohexane, a group in which at least one hydrogen atom has been removed from a polycycloalkane such as adamantane, norbornane, isoborane, tricyclodecane or tetracyclododecane And an alicyclic hydrocarbon group such as a group in which at least one hydrogen atom has been removed. Further, a part of the carbon atoms constituting the ring of the alicyclic hydrocarbon group may be substituted with an ether group (-O-).

Examples of the acid dissociable, dissolution inhibiting group containing an aliphatic cyclic group include, for example,

(i) a carbon skeleton of a monovalent aliphatic cyclic group, a carbon atom bonded to an atom adjacent to the acid dissociable, dissolution inhibiting group (for example, -O- in -C (= O) -O-) A group in which a group or a group other than a hydrogen atom is bonded to form a tertiary carbon atom;

(ii) a group having a monovalent aliphatic cyclic group and a group having a branched-chain alkylene having a tertiary carbon atom bonded thereto, and the like.

In the group of the above (i), the substituent bonded to the carbon atom bonded to the atom adjacent to the cyclic skeleton of the aliphatic cyclic group and the acid dissociable, dissolution inhibiting group includes, for example, an alkyl group. Examples of the alkyl group include the same ones as R ¹⁴ in the following formulas (1-1) to (1-9).

Specific examples of the group of the above (i) include, for example, groups represented by the following general formulas (1-1) to (1-9).

Specific examples of the group (ii) include groups represented by the following general formulas (2-1) to (2-6), and the like.

[Chemical Formula 8]

[Wherein R ¹⁴ is an alkyl group and g is an integer of 0 to 8]

[Chemical Formula 9]

[Wherein R < ¹⁵ > and R < ¹⁶ > are each independently an alkyl group]

The alkyl group for R < ¹⁴ > is preferably a linear or branched alkyl group.

The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group and an n-pentyl group. Of these, a methyl group, an ethyl group or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.

The branched alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. Specific examples thereof include isopropyl, isobutyl, tert-butyl, isopentyl and neopentyl groups, and is most preferably isopropyl.

g is preferably an integer of 0 to 3, more preferably an integer of 1 to 3, and still more preferably 1 or 2.

Examples of the alkyl group of R ¹⁵ to R ^{16 include} the same alkyl groups as those of R ¹⁴ .

In the formulas (1-1) to (1-9) and (2-1) to (2-6), some of the carbon atoms constituting the ring may be substituted with an etheric oxygen atom (-O-) .

In the formulas (1-1) to (1-9), (2-1) to (2-6), hydrogen atoms bonded to the carbon atoms constituting the ring may be substituted with substituents. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, and a fluorinated alkyl group.

The "acetal-type acid dissociable, dissolution inhibiting group" is generally substituted with a hydrogen atom at the terminal of an alkali-soluble group such as a carboxyl group or a hydroxyl group, and is bonded to an oxygen atom. When an acid is generated by exposure, the acid acts to break the bond between the acetal-type acid dissociable, dissolution inhibiting group and the oxygen atom bonded to the acetal-type acid dissociable, dissolution inhibiting group.

Examples of the acetal-type acid dissociable, dissolution inhibiting group include groups represented by the following general formula (p1).

[Chemical formula 10]

Wherein R ^{1 '} and R ^2' each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, n represents an integer of 0 to 3, Y represents an alkyl group having 1 to 5 carbon atoms or an aliphatic cyclic group Indicates]

In the formula (p1), n is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 0.

Examples of the alkyl group represented by R ^{1 '} and R ^2' include the same alkyl groups exemplified as the substituent at the α-position in the description of the acrylic acid ester, preferably a methyl group or an ethyl group, and most preferably a methyl group.

In the present invention, it is preferable that at least one of R ^{1 '} and R ^2' is a hydrogen atom. That is, it is preferable that the acid dissociable, dissolution inhibiting group (p1) is a group represented by the following general formula (p1-1).

(11)

[Wherein R ^{1 '} , n and Y are as defined above]

Examples of the alkyl group for Y include the same alkyl groups exemplified as the substituent at the? -Position in the description of the acrylic acid ester.

The aliphatic cyclic group of Y can be appropriately selected from among a large number of monocyclic or polycyclic aliphatic cyclic groups proposed in the conventional ArF resists and the like. For example, the above-mentioned "acid dissociable dissolution inhibiting group containing an aliphatic cyclic group" May be the same as the aliphatic cyclic groups exemplified in < RTI ID = 0.0 >

The acetal-type acid dissociable, dissolution inhibiting group may be a group represented by the following general formula (p2).

[Chemical Formula 12]

Wherein R ¹⁷ and R ¹⁸ are each independently a linear or branched alkyl group or a hydrogen atom; R ¹⁹ is a linear, branched, or cyclic alkyl group. Or R ¹⁷ and R ¹⁹ are each independently a linear or branched alkylene group and the terminal of R ^{17 and} the terminal of R ¹⁹ may be bonded to form a ring]

In R ¹⁷ and R ¹⁸ , the number of carbon atoms in the alkyl group is preferably from 1 to 15, and may be any of a linear chain and a branched chain, preferably an ethyl group and a methyl group, and most preferably a methyl group. Particularly, it is preferable that one of R ¹⁷ and R ¹⁸ is a hydrogen atom and the other is a methyl group.

R ¹⁹ is a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, and may be any of linear, branched or cyclic.

When R < ¹⁹ > is a linear or branched chain, it preferably has 1 to 5 carbon atoms, more preferably an ethyl group and a methyl group, and most preferably an ethyl group.

When R ¹⁹ is cyclic, it preferably has 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane, or a tetracycloalkane, which may be substituted with a fluorine atom or a fluorinated alkyl group, For example. Specific examples thereof include a monocycloalkane such as cyclopentane and cyclohexane, a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane And the like. Among them, a group obtained by removing at least one hydrogen atom from adamantane is preferable.

In the above formula (p2), R ¹⁷ and R ¹⁹ each independently represents a linear or branched alkylene group (preferably an alkylene group having 1 to 5 carbon atoms), and the terminal of R ¹⁹ and R ¹⁷ May be connected to each other.

In this case, a cyclic group is formed by the oxygen atom to which R ¹⁷ , R ¹⁹ and R ¹⁹ are bonded, and the oxygen atom and the carbon atom to which R ¹⁷ is bonded. The cyclic group is preferably a 4- to 7-membered ring, and more preferably a 4- to 6-membered ring. Specific examples of the cyclic group include a tetrahydropyranyl group, a tetrahydrofuranyl group, and the like.

More specific examples of the structural unit (a1) include a structural unit represented by the following general formula (a1-0-1), a structural unit represented by the following general formula (a1-0-2), and the like.

[Chemical Formula 13]

Wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms; X ¹ is an acid dissociable dissolution inhibiting group; Y ² is a divalent linking group; X ² is an acid dissociable dissolution inhibiting group]

In the general formula (a1-0-1), the alkyl group and the halogenated alkyl group for R are the same as the alkyl group and the halogenated alkyl group exemplified as the substituent at the? -Position in the above description of the acrylate ester. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluorinated alkyl group having 1 to 5 carbon atoms, and most preferably a hydrogen atom or a methyl group.

X ¹ is not particularly limited as long as it is an acid dissociable, dissolution inhibiting group, and examples thereof include the above-mentioned tertiary alkyl ester-type acid dissociable, dissolution inhibiting group and acetal-type acid dissociable, dissolution inhibiting group. An ester-type acid dissociable, dissolution inhibiting group is preferable.

In the general formula (a1-0-2), R is as defined above.

X ² is the same as X ¹ in the formula (a1-0-1).

The divalent linking group of Y ² is not particularly limited, but preferred examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a heteroatom.

The "hydrocarbon group having a substituent" means that a part or all of the hydrogen atoms in the hydrocarbon group are substituted with groups or atoms other than hydrogen atoms.

The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually saturated.

More specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing a ring in the structure.

The linear or branched hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, further preferably 1 to 5 carbon atoms, and most preferably 1 to 2 carbon atoms.

As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specific examples thereof include a methylene group [-CH ₂ -], an ethylene group [- (CH ₂ ) ₂ -] and a trimethylene group [- CH ₂ ) ₃ -], tetramethylene group [- (CH ₂ ) ₄ -], pentamethylene group [- (CH ₂ ) ₅ -] and the like.

Aliphatic hydrocarbon group of the branched, with preferably an alkylene group of branched, and _{specifically, -CH (CH 3) -,} -CH (CH 2 CH 3) -, -C (CH 3) 2 -, _{-C (CH 3) (CH 2} CH 3) -, -C (CH 3) (CH 2 CH 2 CH 3) -, -C (CH 2 CH 3) 2 - a methylene group, such as alkyl; -CH (CH _{3) CH 2 -, -CH (} CH 3) CH (CH 3) -, -C (CH 3) 2 CH 2 -, -CH (CH 2 CH 3) CH 2 -, -CH (CH 2 CH 3) _{CH 2 -, -C (CH 2} CH 3) 2 CH 2 - alkyl group such as _{ethylene; -CH (CH 3) CH 2} CH 2 -, -CH 2 CH (CH 3) CH 2 - such as the alkyl trimethylene And alkyl alkylene groups such as an alkyltetramethylene group such as -CH (CH ₃ ) CH ₂ CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) CH ₂ CH ₂ - and the like. As the alkyl group in the alkyl alkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).

Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), an alicyclic hydrocarbon group bonded to the terminal of the aforementioned chain aliphatic hydrocarbon group, And a group interposed in the middle of a hydrocarbon group.

The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.

The alicyclic hydrocarbon group may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane having 3 to 6 carbon atoms, and examples of the monocycloalkane include cyclopentane, cyclohexane, and the like. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane having 7 to 12 carbon atoms. Specific examples of the polycycloalkane include adamantane, norbornane, isoborane, tri Cyclodecane, tetracyclododecane and the like.

The alicyclic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).

The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring. The number of carbon atoms of the aromatic hydrocarbon group is preferably from 3 to 30, more preferably from 5 to 30, still more preferably from 5 to 20, particularly preferably from 6 to 15, most preferably from 6 to 12. Provided that the number of carbon atoms does not include the number of carbon atoms in the substituent.

Specific examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group and a phenanthryl group. An arylalkyl group such as a phenyl group, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group and a 2-naphthylethyl group. The number of carbon atoms of the alkyl chain in the arylalkyl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

The aromatic hydrocarbon group may have a substituent. For example, some of the carbon atoms constituting the aromatic ring of the aromatic hydrocarbon group may be substituted with a hetero atom, and hydrogen atoms bonded to the aromatic ring of the aromatic hydrocarbon group may be substituted by a substituent.

Examples of the former include a heteroaryl group in which a part of the carbon atoms constituting the ring of the aryl group is substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, a part of carbon atoms constituting the aromatic hydrocarbon ring in the arylalkyl group Is a heteroarylalkyl group substituted by the above-mentioned hetero atom.

Examples of the substituent of the aromatic hydrocarbon group in the latter examples include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and an oxygen atom (= O).

The alkyl group as a substituent of the aromatic hydrocarbon group is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.

The alkoxy group as a substituent of the aromatic hydrocarbon group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, And a methoxy group and an ethoxy group are most preferable.

Examples of the halogen atom as a substituent of the aromatic hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

Examples of the halogenated alkyl group as a substituent of the aromatic hydrocarbon group include groups in which a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom.

The hetero atom in the "divalent linking group containing a hetero atom" is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom.

Specific examples of the divalent linking group containing a heteroatom include -O-, -C (= O) -, -C (= O) -O-, a carbonate bond (-OC -S (= O) ₂ -, -S (= O) ₂ -O-, -NH-, -NR ⁰⁴ (R ⁰⁴ is a substituent such as an alkyl group or an acyl group) = O) -, = N-, and a combination of at least one of these non-hydrocarbon groups with a divalent hydrocarbon group. The divalent hydrocarbon group may be the same as the above-described divalent hydrocarbon group which may have a substituent, and is preferably a linear or branched aliphatic hydrocarbon group.

The divalent linking group for Y ² is preferably a linear or branched alkylene group, a divalent alicyclic hydrocarbon group or a divalent linking group containing a hetero atom. Among them, a linear or branched alkylene group or a divalent linking group containing a hetero atom is preferable.

When Y ² is an alkylene group, the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, most preferably 1 to 3 carbon atoms . Specifically, the same groups as those of the linear alkylene group and branched-chain alkylene group exemplified above can be mentioned.

When Y ² is a divalent alicyclic hydrocarbon group, the alicyclic hydrocarbon group includes the same alicyclic hydrocarbon groups exemplified for the "aliphatic hydrocarbon group containing a ring in the structure".

The alicyclic hydrocarbon group is particularly preferably a group in which two or more hydrogen atoms have been removed from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, and tetracyclododecane.

When Y ² is a divalent linking group containing a hetero atom, preferred examples of the linking group include -O-, -C (= O) -O-, -C (= O) -, -OC -, -C (= O) -NH- , -NH- (H may be substituted with a substituent such as an alkyl group, an acyl group), -S-, -S (= O ) 2 -, -S (= O ) ₂ -O-, the formula -AOB-, - groups of the formula shown in [AC (= O) -O] m -B- or -AOC (= O) -B-, a and B are each independently A bivalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m is an integer of 0 to 3].

When Y ² is -NH-, H may be substituted with a substituent such as an alkyl group or an aryl group (aromatic group). The substituent (alkyl group, aryl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.

In the formula -AOB-, - [AC (= O) -O] _m -B- or -AOC (= O) -B-, A and B are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include those exemplified above as the "divalent hydrocarbon group which may have a substituent" in Y ² .

As A, a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or an ethylene group is particularly preferable.

As the group B, a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group or an alkylmethylene group is more preferable. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.

In the group represented by the formula - [AC (= O) -O] _m -B-, m is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, Do.

The divalent linking group containing a hetero atom is preferably a group having a straight-chain group having an oxygen atom as a hetero atom, for example, a group containing an ether bond or an ester bond, and the formula -AOB-, - [ O) -O] _m -B- or -AOC (= O) -B-.

Among them, the group represented by the formula -AOB- or - [AC (= O) -O] _m -B- is preferable, the group represented by the formula - [AC (= O) -O] _m- M is more preferably 1, and a group represented by - (CH ₂ ) _a -C (═O) -O- (CH ₂ ) _b - is particularly preferable.

a is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, more preferably 1 or 2, and most preferably 1.

b is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, more preferably 1 or 2, and most preferably 1.

More specific examples of the structural unit (a1) include structural units represented by the following general formulas (a1-1) to (a1-4).

[Chemical Formula 14]

Wherein R, R ^{1 '} , R ^2' , n, Y and Y ² are the same as defined above and X 'represents a tertiary alkyl ester-type acid dissociable, dissolution inhibiting group,

In the formulas, X 'is the same as the above-mentioned tertiary alkyl ester-type acid dissociable, dissolution inhibiting group.

R ^{1 ',} R ^2', n, Y roneun R ^{1 ',} R ^2' in the general formula (p1) exemplified in the explanation of "acetal-type acid dissociable, dissolution inhibiting group" described above, respectively, n, Y And the like.

Y ² is the same as Y ² in the general formula (a1-0-2) described above.

Specific examples of the structural units represented by the general formulas (a1-1) to (a1-4) are shown below.

In the following formulas, R ^{? Represents} a hydrogen atom, a methyl group or a trifluoromethyl group.

[Chemical Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

(A1-0-11), a structural unit represented by the following general formula (a1-0-12), a structural unit represented by the following general formula (a1-0- 13) and a structural unit represented by the following general formula (a1-0-2). Among them, a structural unit represented by the formula (a1-0-11), a structural unit represented by the following formula (a1-0-12) and a structural unit represented by the following formula (a1-0-2) It is preferable to have at least one species.

[Chemical Formula 22]

Wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, R ²¹ is an alkyl group, and R ²² forms an aliphatic monocyclic group together with the carbon atom to which the R ²² is bonded R ²³ is a branched alkyl group, R ²⁴ is a group forming an aliphatic polycyclic group together with the carbon atom to which R ²⁴ is bonded, and R ²⁵ is a linear alkyl group having 1 to 5 carbon atoms. Y ² is a divalent linking group, and X ² is an acid dissociable dissolution inhibiting group]

In the formulas, R, Y ² , and X ² are the same as described above.

Examples of the alkyl group represented by R ^{21 in} the general formula (a1-0-11) include the same alkyl groups represented by R ^{14 in} the above formulas (1-1) to (1-9), and a methyl group, an ethyl group or an isopropyl group desirable.

The aliphatic monocyclic sentence to R ²² form together with the carbon atom art R ²² is bonded, there may be mentioned that the tertiary alkyl ester-type acid dissociable, the same as that of, monocyclic sentence of the aliphatic cyclic group exemplified in groups dissolution inhibiting group. Specific examples thereof include groups in which one or more hydrogen atoms have been removed from a monocycloalkane. The monocycloalkane is preferably a 3 to 11-membered ring, more preferably 3 to 8-membered ring, further preferably 4 to 6-membered ring, and particularly preferably 5-membered or 6-membered ring.

The monocycloalkane may be partially substituted with an ether group (-O-) or may not be substituted with carbon atoms constituting the ring.

The monocycloalkane may have an alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a fluorinated alkyl group having 1 to 5 carbon atoms as a substituent.

Examples of R ²² constituting the aliphatic monocyclic group include linear alkylene groups in which an ether group (-O-) may intervene between carbon atoms.

Specific examples of the structural unit represented by the formula (a1-0-11) include the structural units represented by the above formulas (a1-1-16) to (a1-1-23), (a1-1-27), (a1-1-31 ). ≪ / RTI > Among them, the compounds represented by formulas (a1-1-16) to (a1-1-17), (a1-1-20) to (a1-1-23), (a1-1-27), (a1-1-31 Is preferably a structural unit represented by the following formula (a1-1-02). The structural unit represented by the following (a1-1-02 ') is also preferable.

In the formula, h is preferably 1 or 2.

(23)

(Wherein R and R ²¹ are each the same as defined above, and h is an integer of 1 to 3)

Examples of the branched alkyl group represented by R ^{23 in} the formula (a1-0-12) include the same as the branched alkyl group represented by R ¹⁴ in the formulas (1-1) to (1-9) And isopropyl group is most preferable.

That R ²⁴ is the art R ²⁴ is an aliphatic formed with a combination of carbon atoms, polycyclic groups, the first can be given as those resulting from a tertiary alkyl ester-type acid dissociable, of the aliphatic cyclic group exemplified in groups dissolution inhibiting polycyclic the same.

Specific examples of the structural unit represented by the formula (a1-0-12) include structural units represented by the above formulas (a1-1-26), (a1-1-28) to (a1-1-30) have.

A structural unit represented by the formula (a1-0-12) is a, R ²⁴ a, R ²⁴ is art aliphatic polycyclic group 2 to form together with the carbon atom bonded adamantyl group is preferred, and particularly, the above formula (a1 -1-26) is preferable.

In the formula (a1-0-13), R and R ²⁴ are each the same as defined above.

Examples of the linear alkyl group for R ²⁵ include the same linear alkyl groups as exemplified for the alkyl group for R ^{14 in} the above formulas (1-1) to (1-9), and most preferably a methyl group or ethyl group .

Specific examples of the structural unit represented by the formula (a1-0-13) include structural units represented by the general formulas (a1-1-1) to (a1-1-2), (a1-1-2), include structural units represented by the following formulas (a1-1-7) to (a1-1-15).

A structural unit represented by the following formula (a1-0-13) is a, R ²⁴ a, R ²⁴ is art aliphatic polycyclic group 2 to form together with the carbon atom bonded adamantyl group is preferred, and particularly, the above formula (a1 -1-1) or (a1-1-2) is preferable.

Examples of the structural unit represented by the formula (a1-0-2) include a structural unit represented by the above formula (a1-3) or (a1-4), particularly preferably a structural unit represented by the formula (a1-3) Do.

As the structural unit represented by formula (a1-0-2), it is particularly preferable that Y ² in the formula is a group represented by -AOB- or -AC (= O) -OB-.

Preferable examples of such a structural unit include a structural unit represented by the following general formula (a1-3-01); A structural unit represented by the following general formula (a1-3-02); Structural units represented by the following general formula (a1-3-03), and the like.

≪ EMI ID =

Wherein R is the same as above, R ¹³ is a hydrogen atom or a methyl group, R ¹⁴ is an alkyl group, a is an integer of 1 to 10, and n 'is an integer of 0 to 3,

(25)

Wherein X is an acid dissociable dissolution inhibiting group and n is an integer of 0 to 3, wherein R is as defined above, Y ^{2 '} and Y ^{2 "} are each independently a divalent linking group,

In the formulas (a1-3-01) ~ (a1-3-02), R 13 is preferably a hydrogen atom.

R ¹⁴ is the same as R ¹⁴ in the formula (1-1) to (1-9).

a is preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and most preferably 1 or 2.

n 'is preferably 1 or 2, and most preferably 2.

Specific examples of the structural unit represented by the formula (a1-3-01) include structural units represented by the above formulas (a1-3-25) to (a1-3-26).

Specific examples of the structural unit represented by the formula (a1-3-02) include structural units represented by the above formulas (a1-3-27) to (a1-3-28).

In the formula (a1-3-03), the divalent linking group in Y ^{2 '} and Y ^{2 "} includes the same groups as Y ² in the general formula (a1-3).

As Y ^{2 '} , a divalent hydrocarbon group which may have a substituent is preferable, and a linear aliphatic hydrocarbon group is more preferable, and a linear alkylene group is more preferable. Among them, a linear alkylene group having 1 to 5 carbon atoms is preferable, and a methylene group and an ethylene group are most preferable.

Y ^{2 "} is preferably a divalent hydrocarbon group which may have a substituent, more preferably a linear aliphatic hydrocarbon group, and more preferably a linear alkylene group. Among them, a linear, An alkylene group is preferable, and a methylene group and an ethylene group are most preferable.

The acid dissociable, dissolution inhibiting group in X 'is the same as described above, and is preferably a tertiary alkyl ester-type acid dissociable, dissolution inhibiting group, and the aforementioned (i) A group in which a substituent is bonded to a carbon atom bonded to an atom adjacent to the acid dissociable, dissolution inhibiting group to form a tertiary carbon atom is more preferable, and the group represented by the general formula (1-1) is particularly preferable.

n is an integer of 0 to 3, n is preferably an integer of 0 to 2, more preferably 0 or 1, and most preferably 1.

The structural unit represented by the formula (a1-3-03) is preferably a structural unit represented by the following general formula (a1-3-03-1) or (a1-3-03-2) -3-03-1) is preferable.

(26)

Wherein R and R ¹⁴ are the same as defined above, a is an integer of 1 to 10, b is an integer of 1 to 10, and t is an integer of 0 to 3,

Among the formulas (a1-3-03-1) to (a1-3-03-2), a is preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and most preferably 1 or 2 .

b is preferably an integer of 1 to 8, more preferably an integer of 1 to 5, and particularly preferably 1 or 2.

t is preferably an integer of 1 to 3, and 1 or 2 is particularly preferable.

Specific examples of the structural unit represented by the formula (a1-3-03-1) or (a1-3-03-2) include structural units represented by the above formulas (a1-3-29) to (a1-3-32) Unit.

As the structural unit (a1), one type may be used alone, or two or more types may be used in combination.

In particular, it is preferable that at least two kinds of the structural units (a1) are used in view of good lithography characteristics. When the component (A1) has at least two structural units (a1), the number of the structural units (a1) is preferably 2 to 4, more preferably 2 or 3.

(A1-0-11), the structural unit represented by the general formula (a1-0-12), the structural unit represented by the general formula (a1-0-13), the structural unit represented by the general formula , And a constituent unit represented by the general formula (a1-0-2).

In this case, the at least two kinds of structural units (a1) include structural units represented by the general formula (a1-0-11), structural units represented by the general formula (a1-0-12), structural units represented by the general formulas (a1- 0-13) and the structural unit represented by the general formula (a1-0-2), and may be composed of at least one kind of these structural units and a structural unit represented by the general formula Or may be a combination with other structural unit (a1).

Examples of the other structural unit (a1) include a structural unit represented by the general formula (a1-2), a structural unit represented by the general formula (a1-4), and the like.

The proportion of the structural unit (a1) in the component (A1) is preferably from 10 to 80 mol%, more preferably from 20 to 70 mol%, and still more preferably from 25 to 50 mol% based on the total structural units constituting the component (A1) Mol% is more preferable. By setting it to the lower limit value or more, a pattern can easily be obtained when the resist composition is used, and when it is not more than the upper limit value, balance with other constituent units can be obtained.

(The constituent unit (a2))

A structural unit (a2) is -SO ₂ - content (called hereinafter, the constituent unit (a2 ^S)) and a configuration derived from an acrylate ester containing a lactone-containing cyclic group unit a structural unit derived from an acrylate ester containing a cyclic group is at least one kind of structural unit selected from the group consisting of (hereinafter referred to as structural unit (a2 ^L)).

A structural unit (a2) is -SO ₂ - by containing a cyclic group or a lactone-containing cyclic group, increase the adhesion to the resist film to the substrate is formed using a positive resist composition containing the art (A1) component, or water By enhancing the affinity with a developing solution containing it, it contributes to the improvement of the lithography characteristics.

, The constituent unit (a2 ^S):

A structural unit (a2 ^S) is -SO ₂ - is a structural unit derived from an acrylate ester containing a cyclic group containing.

Here, -SO ₂ - containing (a sulfur atom (S) in the ring which forms part of the ring backbone that is -SO ₂₎ - containing cyclic group is, and -SO ₂ in the ring skeleton ring containing And when the ring is only a ring, it is a monocyclic ring, and when it has a ring structure of any other ring, it is called a ring ring regardless of its structure. The -SO ₂ -containing cyclic group may be monocyclic or polycyclic.

-SO ₂ - containing cyclic group are, in particular, those in the ring skeleton -O-SO ₂ - containing cyclic group, i.e. -O-SO ₂ - -OS- a sultone (sultone) ring which forms part of the ring skeleton of .

The -SO ₂ -containing cyclic group preferably has 3 to 30 carbon atoms, preferably 4 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, and particularly preferably 4 to 12 carbon atoms. Provided that the number of carbon atoms is the number of carbon atoms constituting the ring skeleton and does not include the number of carbon atoms in the substituent.

The -SO ₂ -containing cyclic group may be an -SO ₂ -containing aliphatic cyclic group or an -SO ₂ -containing aromatic cyclic group. Preferably a -SO ₂ -containing aliphatic cyclic group.

Examples of the -SO ₂ -containing aliphatic cyclic group include groups in which at least one hydrogen atom is removed from an aliphatic hydrocarbon ring in which a part of the carbon atoms constituting the cyclic backbone is replaced by -SO ₂ - or -O-SO ₂ - have. More specifically, a group in which at least one hydrogen atom is removed from an aliphatic hydrocarbon ring in which -CH ₂ - constituting the ring skeleton is substituted with -SO ₂ -, a group in which -CH ₂ -CH ₂ - And groups obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring substituted with O-SO ₂ -.

The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.

The alicyclic hydrocarbon group may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane having 3 to 6 carbon atoms, and examples of the monocycloalkane include cyclopentane, cyclohexane, and the like. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane having 7 to 12 carbon atoms. Specific examples of the polycycloalkane include adamantane, norbornane, isoborane, tri Cyclodecane, tetracyclododecane and the like.

The -SO ₂ -containing cyclic group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxygen atom (═O), -COOR ", -OC (═O) R", a hydroxyalkyl group, .

The alkyl group as the substituent is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably a linear or branched chain. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl and hexyl. Among them, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

The alkoxy group as the substituent is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably a linear or branched chain. Specifically, a group bonded to an oxygen atom (-O-) to an alkyl group exemplified as an alkyl group as the above substituent can be mentioned.

Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

The halogenated alkyl group of the substituent includes a group in which a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom.

Examples of the halogenated alkyl group as the substituent include groups in which a part or all of the hydrogen atoms of the alkyl group exemplified as the alkyl group as the substituent are substituted with the halogen atom. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

R "in the above -COOR" and -OC (═O) R "is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms.

When R "is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, particularly preferably a methyl group or an ethyl group.

When R "is a cyclic alkyl group, the number of carbon atoms is preferably from 3 to 15, more preferably from 4 to 12, and most preferably from 5 to 10. Specific examples thereof include a fluorine atom or a fluorinated alkyl group A group in which one or more hydrogen atoms have been removed from a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane, or a tetracycloalkane, which may be substituted or not may be exemplified. More specifically, A monocycloalkane such as cyclopentane or cyclohexane, a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isoborane, tricyclodecane or tetracyclododecane, and the like have.

As the hydroxyalkyl group as the substituent, the number of carbon atoms is preferably from 1 to 6, and specific examples include groups in which at least one hydrogen atom of the alkyl group exemplified as the alkyl group as the substituent is substituted with a hydroxyl group.

More specific examples of the -SO ₂ -containing cyclic group include the groups represented by the following general formulas (3-1) to (3-4).

(27)

Wherein A 'is an alkylene group, an oxygen atom or a sulfur atom having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, z is an integer of 0 to 2, R ⁶ is an alkyl group, an alkoxy group, (= O) R ", a hydroxyalkyl group or a cyano group, and R" is a hydrogen atom or an alkyl group]

In general formulas (3-1) to (3-4), A 'represents an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-), an oxygen atom or Sulfur atom.

The alkylene group having 1 to 5 carbon atoms in A 'is preferably a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, an n-propylene group and an isopropylene group.

When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include a group in which -O- or -S- is interposed between the terminal or carbon atom of the alkylene group, and examples thereof include -O -CH ₂ -, -CH ₂ -O-CH ₂ -, -S-CH ₂ -, -CH ₂ -S-CH ₂ - and the like.

As A ', an alkylene group having 1 to 5 carbon atoms or -O- is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group is most preferable.

z may be any of 0 to 2, with 0 being most preferred.

When z is 2, a plurality of R ^{6 s} may be the same or different.

An alkyl group, an alkoxy group, a halogenated alkyl group, -COOR in ^{R 6 ", -OC (= O} ) R", a hydroxyl group, respectively, -SO ₂ In the above-exemplified as the substituent which may contain a cyclic group with An alkyl group, an alkoxy group, a halogenated alkyl group, -COOR ", -OC (= O) R", and a hydroxyalkyl group.

Specific cyclic groups represented by the above general formulas (3-1) to (3-4) are exemplified below. In the formulas, " Ac " represents an acetyl group.

(28)

[Chemical Formula 29]

(30)

(31)

(32)

As the -SO ₂ -containing cyclic group, the group represented by the general formula (3-1) is preferable among the above, and the groups represented by the general formulas (3-1-1), (3-1-18), (3-3-1 ) And (3-4-1), and most preferably a group represented by the formula (3-1-1).

As an example of the structural unit (a2 ^S), there may be mentioned a structural unit represented by the more specific, the following formula (a2-0).

(33)

Wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, R ⁵ is a -SO ₂ -containing cyclic group, and R ²⁹ is a single bond or a divalent linking group.

In the formula (a2-0), R is as defined above.

R ⁵ is the same as the -SO ₂ -containing cyclic group exemplified above.

R ²⁹ may be a single bond or a divalent linking group. It is preferably a divalent linking group in that the effect of the present invention is excellent.

The divalent linking group for R ²⁹ is not particularly limited and includes, for example, as a divalent linking group in Y ² in the general formula (a1-0-2) exemplified in the description of the structural unit (a1) The same thing as the one can be cited. Among them, an alkylene group or an ester bond (-C (= O) -O-) is preferable.

The alkylene group is preferably a linear or branched alkylene group. Specifically, the same groups as the linear alkylene group and branched-chain alkylene group exemplified as the aliphatic hydrocarbon group in Y ² can be mentioned.

The divalent linking group containing an ester bond is preferably a group represented by the general formula: -R ⁴ -C (= O) -O- [wherein R ⁴ is a divalent linking group]. That is, it is preferable that the structural units represented by the following general formula (a2-0-1) a structural unit (a2 ^S).

(34)

[Wherein R and R ⁵ are each the same as defined above, and R ⁴ is a divalent linking group]

R ⁴ is not particularly limited, and for example, the same groups as those exemplified as the divalent linking group in Y ² in the general formula (a1-0-2) exemplified in the description of the structural unit (a1) can be mentioned .

As the divalent linking group for R ⁴ , a linear or branched alkylene group, a divalent alicyclic hydrocarbon group, or a divalent linking group containing a hetero atom is preferable.

The linear or branched alkylene group, a divalent alicyclic hydrocarbon group, a divalent connecting group containing a hetero atom are, respectively, preferred a linear or alkylene group of branched illustrated as in the Y ^2, A divalent alicyclic hydrocarbon group, and a divalent linking group containing a hetero atom.

Among them, a linear or branched alkylene group or a divalent linking group containing an oxygen atom as a hetero atom is preferable.

As the linear alkylene group, a methylene group or an ethylene group is preferable, and a methylene group is particularly preferable.

As the branched alkylene group, an alkylmethylene group or an alkylethylene group is preferable, and -CH (CH ₃ ) -, -C (CH ₃ ) ₂ - or -C (CH ₃ ) ₂ CH ₂ - .

The divalent linking group containing an oxygen atom is preferably a divalent linking group containing an ether linkage or an ester linkage and is preferably a linking group represented by the formula -AOB-, - [AC (= O) -O] _m -B- or -AOC = O) -B- is more preferable.

Among them, a group represented by the formula -OC (= O) -B- is preferable, and a group represented by - (CH ₂ ) _c --C (═O) -O- (CH ₂ ) _d - is particularly preferable. c is an integer of 1 to 5, preferably 1 or 2. d is an integer of 1 to 5, preferably 1 or 2.

A structural unit (a2 ^S) roneun In particular, the following general formula (a0-1-11) or the structural units represented by (a0-1-12) are preferred, more preferably a constituent unit represented by the formula (a0-1-12) Do.

(35)

[Wherein R, A ', R ⁶ , z and R ⁴ are each as defined above]

In the formula (a0-1-11), it is preferable that A 'is a methylene group, an oxygen atom (-O-) or a sulfur atom (-S-).

As R ⁴ , a linear or branched alkylene group or a divalent linking group containing an oxygen atom is preferable. The bivalent connecting group containing an alkylene group or an oxygen atom in the linear or branched alkylene group and the branched alkylene group in R ⁴ is preferably a linear or branched alkylene group or a divalent The same as the connector.

As the structural unit represented by the formula (a0-1-12), a structural unit represented by the following general formula (a0-1-12a) or (a0-1-12b) is particularly preferable.

(36)

Wherein R and A 'are each the same as defined above, and c to e are each independently an integer of 1 to 3,

Constituent unit (a2 ^L ):

The structural unit (a2 ^L ) is a structural unit derived from an acrylate ester containing a lactone-containing cyclic group.

Here, the lactone-containing cyclic group means a cyclic group containing a ring (lactone ring) containing -O-C (O) - in its cyclic skeleton. When the lactone ring is counted as the first ring, only the lactone ring is referred to as a monocyclic ring, and in the case of other ring structures, it is referred to as a polycyclic ring regardless of its structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.

The lactone cyclic group in the structural unit (a2 ^L ) is not particularly limited, and any of them may be used. Specifically, examples of the lactone-containing monocyclic group include groups in which one hydrogen atom has been removed from a 4- to 6-membered ring lactone, for example, a group in which one hydrogen atom has been removed from? -Propiolactone, A group in which one atom is removed, and a group in which one hydrogen atom is removed from? -Valerolactone. Examples of the lactone-containing polycyclic group include groups in which one hydrogen atom has been removed from a bicycloalkane, tricycloalkane or tetracycloalkane having a lactone ring.

Examples of the structural unit (a2 ^L) is, for example, the formula (a2-0) can be mentioned that the replacement of the R ⁵ to lactone-containing cyclic group, more specifically, the general formula (a2-1) To (a2-5).

(37)

Wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms; R 'each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or -COOR ", and R "is a hydrogen atom or an alkyl group; R ²⁹ is a single bond or a divalent linking group; s "is an integer of 0 to 2; A" is an alkylene group, an oxygen atom or a sulfur atom of 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom; m is 0 or 1;

R in the general formulas (a2-1) to (a2-5) is the same as R in the structural unit (a1).

Examples of the alkyl group having 1 to 5 carbon atoms for R 'include a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group.

Examples of the alkoxy group having 1 to 5 carbon atoms for R 'include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, a n-butoxy group and a tert-butoxy group.

R 'is preferably a hydrogen atom in consideration of industrial availability.

The alkyl group in R "may be linear, branched or cyclic.

When R "is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

When R "is a cyclic alkyl group, the number of carbon atoms is preferably from 3 to 15, more preferably from 4 to 12, and most preferably from 5 to 10. Specific examples thereof include a fluorine atom or a fluorinated alkyl group A group obtained by removing one or more hydrogen atoms from a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane, or a tetracycloalkane, which may be substituted or unsubstituted, and the like. A monocycloalkane such as pentane or cyclohexane, or a group in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isoborane, tricyclodecane or tetracyclododecane .

A "represents an alkylene group having 1 to 5 carbon atoms, an oxygen atom (-O-), or a sulfur atom (-S-), for example, More preferably an alkylene group having 1 to 5 carbon atoms or -O-. As the alkylene group having 1 to 5 carbon atoms, a methylene group or a dimethylmethylene group is more preferable, and a methylene group is most preferable.

R ²⁹ is the same as R ²⁹ in the formula (a2-0).

In formula (a2-1), s "is preferably 1 to 2.

Specific examples of the structural units represented by the general formulas (a2-1) to (a2-5) are exemplified below. In the following formulas, R ^{? Represents} a hydrogen atom, a methyl group or a trifluoromethyl group.

(38)

[Chemical Formula 39]

(40)

(41)

(42)

A structural unit (a2 ^L) roneun, the formula preferably at least one member selected from the group consisting of structural units represented by (a2-1) ~ (a2-5) and the formula (a2-1) ~ (a2-3 ), And at least one member selected from the group consisting of structural units represented by the general formula (a2-1) or (a2-2) is particularly preferable.

Among them, the compounds represented by the above formulas (a2-1-1), (a2-1-2), (a2-2-1), (a2-2-7), (a2-2-12) 14), (a2-3-1), and (a2-3-5).

In the component (A1), as the structural unit (a2), one type may be used alone, or two or more types may be used in combination. For example, as a structural unit (a2), and may use only the constituent unit (a2 ^S), and may use only the constituent unit (a2 ^L), it may be used together with them. Further, as the structural unit (a2 ^S) or structural unit (a2 ^L), and may be used one kind alone or may be used in combination of two or more.

Those having at least a structural unit (a2 ^S) a In particular, the constituent unit (a2) in the present invention are preferred because of excellent effects of the present invention.

The proportion of the structural unit (a2) in the component (A1) is preferably from 1 to 80 mol%, more preferably from 10 to 70 mol%, based on the total of all the structural units constituting the component (A1) , More preferably from 10 to 65 mol%, and particularly preferably from 10 to 60 mol%. The effect of containing the constituent unit (a2) can be sufficiently obtained by setting the amount to not less than the lower limit value, and if it is not more than the upper limit value, balance with other constituent units can be obtained and various lithographic properties such as MEEF, CDU and pattern shape are improved .

(The constituent unit (a3))

The structural unit (a3) is a structural unit (a3) derived from an acrylate ester containing a polar group-containing aliphatic hydrocarbon group. The component (A1) has the structural unit (a3), so that the hydrophilicity of the component (A) is increased, the affinity with the developer is increased, the alkali solubility in the exposed portion is improved, and the improvement in resolution is contributed.

Examples of the polar group include a hydroxyl group, a cyano group, a carboxyl group, and a fluorinated alcohol group (a hydroxyalkyl group in which a part of the hydrogen atoms of the alkyl group is substituted with a fluorine atom). Among them, a hydroxyl group and a carboxyl group are preferable, and a hydroxyl group is particularly preferable.

In the structural unit (a3), the number of polar groups to be bonded to the aliphatic hydrocarbon group is not particularly limited, but is preferably 1 to 3, and most preferably 1.

The aliphatic hydrocarbon group to which the polar group is bonded may be saturated, unsaturated, or saturated.

More specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing a ring in the structure.

The "linear or branched aliphatic hydrocarbon group" preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, even more preferably 1 to 8 carbon atoms, and even more preferably 1 to 6 carbon atoms.

The linear or branched aliphatic hydrocarbon group may have a part or all of the hydrogen atoms substituted by a substituent other than the polar group. Examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O). The linear or branched aliphatic hydrocarbon group may have a divalent group containing a hetero atom between carbon atoms. As the "divalent group containing a hetero atom", the "divalent group containing a hetero atom" exemplified as a divalent linking group of Y ^{2 in} the general formula (a1-0-2) in the description of the structural unit (a1) Linking group "

When the aliphatic hydrocarbon group is a linear or branched chain type, the structural unit (a3) is preferably a structural unit represented by the following general formula (a3-1) or (a3-2).

(43)

Wherein R is the same as defined above, R ⁸¹ is a linear or branched alkylene group, and R ⁸² is an alkylene group with which a divalent group containing a hetero atom may intervene]

In the formula (a3-1), the alkylene group in R ⁸¹ preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms.

In the formula (a3-2), the alkylene group in R ⁸² preferably has 1 to 12 carbon atoms, more preferably 1 to 10, and particularly preferably 1 to 6 carbon atoms.

When the alkylene group is an alkylene group having 2 or more carbon atoms, a divalent group containing a hetero atom may be interposed between the carbon atoms of the alkylene group. As the "divalent group containing a hetero atom", the "divalent group containing a hetero atom" exemplified as a divalent linking group of Y ^{2 in} the general formula (a1-0-2) in the description of the structural unit (a1) Linking group "

R ⁸² is preferably an alkylene group in which a divalent group containing a hetero atom does not intervene or an alkylene group in which a divalent group containing an oxygen atom as a heteroatom intervenes.

As the alkylene group interposed by a divalent group containing an oxygen atom, a group represented by -A-O-B- or -A-O-C (= O) -B- is preferable. In the formula, A and B are each independently a divalent hydrocarbon group which may have a substituent, and A, B and A in the -AOB- or -AOC (= O) -B- exemplified in the description of the structural unit (a1) B and the like.

Among them, a group represented by -AOC (= O) -B- is preferable, and - (CH ₂ ) _f -OC (= O) - (CH ₂ ) _g - wherein f and g are each independently 1 - Lt; 3 >

As the above-mentioned "aliphatic hydrocarbon group containing a ring in the structure", a cyclic aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group thereof may be bonded to the terminal of the above-mentioned chain-like aliphatic hydrocarbon group, or a middle-chain aliphatic hydrocarbon group And the like.

The cyclic aliphatic hydrocarbon group preferably has 3 to 30 carbon atoms. The cyclic aliphatic hydrocarbon group may be polycyclic, monocyclic or polycyclic.

As the cyclic aliphatic hydrocarbon group, for example, a resin for a resist composition for an ArF excimer laser can be appropriately selected from among many proposed ones. For example, as the monocyclic aliphatic hydrocarbon group, a group obtained by removing two or more hydrogen atoms from a monocycloalkane having 3 to 20 carbon atoms is preferable, and examples of the monocycloalkane include cyclopentane, cyclohexane and the like. The polycyclic aliphatic hydrocarbon group is preferably a group obtained by removing two or more hydrogen atoms from a polycycloalkane having 7 to 30 carbon atoms. Specific examples of the polycycloalkane include adamantane, norbornane, isoborane, tri Cyclodecane, tetracyclododecane and the like.

In the cyclic aliphatic hydrocarbon group, a part or all of the hydrogen atoms may be substituted with a substituent other than the polar group. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxygen atom (= O).

When the aliphatic hydrocarbon group contains a ring in the structure, as the structural unit (a3), a structural unit represented by the following general formula (a3-3), (a3-4) or (a3-5) is preferable.

(44)

R is as defined above, j is an integer of 1 to 3, k 'is an integer of 1 to 3, t' is an integer of 1 to 3, 1 'is an integer of 1 to 5, s' is an integer of 1 to 3]

In formula (a3-3), j is preferably 1 or 2, more preferably 1. When j is 2, it is preferable that the hydroxyl group is bonded to the 3-position and the 5-position of the adamantyl group. When j is 1, it is preferable that the hydroxyl group is bonded to the 3-position of the adamantyl group.

In formula (a3-4), k 'is preferably 1. The cyano group is preferably bonded to the 5-position or the 6-position of the norbornyl group.

In the formula (a3-5), t 'is preferably 1. l 'is preferably 1. s' is preferably 1.

In the formula (a3-5), the oxygen atom (-O-) of the carbonyloxy group is preferably bonded to the 2-position or 3-position of the norbornane ring. It is preferable that the fluorinated alkyl alcohol group is bonded to the 5-position or the 6-position of the norbornyl group.

The structural unit (a3) may be used alone or in combination of two or more.

The structural unit (a3) preferably has a structural unit represented by any one of the general formulas (a3-1) to (a3-5), particularly preferably a structural unit represented by the general formula (a3-2) Do.

The proportion of the constituent unit (a3) in the component (A1) is preferably from 1 to 50 mol%, more preferably from 5 to 40 mol%, and still more preferably from 5 to 40 mol% based on the total constituent units constituting the component (A1) More preferably 25 mol%.

(Constituent unit (a4))

The structural unit (a4) is a structural unit derived from an acrylate ester containing an aliphatic cyclic group of acidity. Since the component (A1) has the structural unit (a4), the resist pattern shape becomes favorable.

The "aliphatic cyclic group of the acid-labile group" is an aliphatic cyclic group remaining in the constituent unit without being dissociated even when the acid is generated from the component (B) by exposure.

The aliphatic cyclic group is not particularly limited as long as it is acid-comparable, and is used as a resin component of a resist composition for ArF excimer laser or KrF excimer laser (preferably for ArF excimer laser) Can be used. The aliphatic cyclic group may be saturated, unsaturated, or saturated. Specifically, there may be mentioned a group obtained by removing one hydrogen atom from a cycloalkane such as monocycloalkane, polycycloalkane and the like exemplified in the description of the aliphatic cyclic group in the aforementioned structural unit (a1).

The aliphatic cyclic group may be monocyclic or polycyclic, and it is preferably polycyclic in that it has excellent effects. In particular, it is preferably a ring having 2 to 4 rings. Among them, at least one ring selected from a tricyclodecyl group, an adamantyl group, a tetracyclododecyl group, an isobornyl group and a norbornyl group is industrially easily available .

Specific examples of the acid-labile aliphatic cyclic group include, for example, a carbon atom (for example, -O- in -C (= O) -O-) bonded to an atom adjacent to the aliphatic cyclic group And a monovalent aliphatic cyclic group in which a substituent (an atom or a group other than a hydrogen atom) is not bonded. Specifically, a group in which R ¹⁴ is substituted with a hydrogen atom in the groups represented by the formulas (1-1) to (1-9) illustrated in the description of the structural unit (a1); And a group in which a hydrogen atom is removed from the tertiary carbon atom of a cycloalkane having a tertiary carbon atom formed only by a carbon atom constituting the ring skeleton.

The aliphatic cyclic group may be substituted with a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a fluorine atom, and a fluorinated alkyl group.

As the structural unit (a4), a structural unit represented by the following general formula (a4-0) is preferable, and a structural unit represented by the following general formulas (a4-1) to (a4-5) is particularly preferable.

[Chemical Formula 45]

[Wherein R is the same as defined above and R ⁴⁰ is an aliphatic polycyclic group having acid-labile properties]

(46)

[Wherein R is as defined above]

As the structural unit (a4), one type may be used alone, or two or more types may be used in combination.

When the structural unit (a4) is contained in (A1), the proportion of the structural unit (a4) in the component (A1) is preferably from 1 to 30 mol% based on the total structural units constituting the component (A1) , And more preferably 5 to 20 mol%.

The component (A1) may contain other constitutional units than the above-mentioned constitutional units (a1) to (a4) so long as the effect of the present invention is not impaired.

The other constituent unit is not particularly limited as long as it is other constituent unit not classified as the above-mentioned constituent units (a1) to (a4), and the constituent units for ArF excimer laser, KrF excimer laser (preferably for ArF excimer laser) A large number of conventionally known ones can be used as the resin for resist.

As the component (A1), a copolymer having the structural units (a0) and (a1) is preferable, and a copolymer having the structural units (a0), (a1) and (a2) is more preferable.

(A0), (a1) and (a2), structural units (a0), (a1) and (a2) (a0), (a1), (a2), (a1), (a2) and (a3) a3) and (a4), and the like.

Preferred examples of the component (A1) include a copolymer having two kinds of constitutional units represented by the following formula (A1-21), a copolymer having three kinds of constitutional units represented by the following formulas (A1-31) to A copolymer having four kinds of structural units respectively represented by the following formulas (A1-41) to (A1-48), a copolymer having five kinds of structural units represented by the following formulas (A1-51) to (A1-54) And the like.

(47)

[Wherein R, R ²⁵ and W are each the same as defined above, and a plurality of R's in the formula may be the same or different]

(48)

Wherein R, R ²⁹ , R ²⁵ and W are the same as defined above, and a plurality of R's in the formula may be the same or different,

(49)

Wherein R, R ²⁹ , A ", R ²⁵ and W are each the same as defined above, and a plurality of R's in the formula may be the same or different,

(50)

Wherein R, R ⁴ , A ', R ²⁵ and W are the same as defined above, and a plurality of R's in the formula may be the same or different,

(51)

Wherein R, R ⁴ , A ', R ²⁵ and W are the same as defined above, and a plurality of R's in the formula may be the same or different,

(52)

Wherein R, A ', R ²⁵ and W are each the same as defined above, and a plurality of R's in the formula may be the same or different,

(53)

Wherein R, R ⁴ , A ', R ²³ and W are the same as defined above, and a plurality of R's in the formula may be the same or different,

(54)

Wherein R, R ⁴ , A ', R ²¹ , h and W are each the same as defined above, and a plurality of R's in the formula may be the same or different,

(55)

Wherein R, R ²⁹ , R ²¹ , h and W are the same as defined above, and a plurality of R's in the formula may be the same or different,

(56)

Wherein R, R ⁴ , A ', R ²³ , a, b, R ¹⁴ and W are the same as defined above, and a plurality of R's in the formula may be the same or different,

(57)

Wherein R, R ⁴ , A ', R ²⁵ , a, b, R ¹⁴ and W are the same as defined above, and a plurality of R's in the formula may be the same or different,

(58)

Wherein R, R ⁴ , A ', R ²³ , R ²⁵ and W are the same as defined above, and a plurality of R's in the formula may be the same or different,

[Chemical Formula 59]

Wherein R, R ²⁹ , R ⁴ , A ', R ²³ and W are the same as defined above, and a plurality of R's in the formula may be the same or different,

(60)

Wherein R, R ²⁹ , R ⁴ , A ', R ²⁵ and W are the same as defined above, and a plurality of R's in the formula may be the same or different,

(61)

Wherein R, R ²⁹ , R ⁴ , A ', R ²¹ , h and W are the same as defined above, and plural R's in the formula may be the same or different,

(62)

Wherein R, R ⁴ , A ', R ²³ , R ²¹ , h and W are the same as defined above, and a plurality of R's in the formula may be the same or different,

(63)

Wherein R, R ²⁹ , R ²⁵ and W are the same as defined above, and a plurality of R's in the formula may be the same or different,

≪ EMI ID =

Wherein R, R ²⁹ , R ⁴ , A ', R ²³ , R ²¹ , h and W are the same as defined above, and a plurality of R's in the formula may be the same or different,

(65)

Wherein R, R ²⁹ , R ⁴ , A ', R ²⁵ , R ²¹ , h and W are the same as defined above, and a plurality of R's in the formula may be the same or different,

(66)

Wherein R, R ²⁹ , R ⁴ , A ', R ²³ , R ²¹ , h, W and R ⁸² are the same as defined above and plural R's may be the same or different,

(67)

Wherein R, e, A ', c, d, R ²³ , a, b, R ¹⁴ and W are the same as defined above, and a plurality of R's and a plurality of A' ]

The mass average molecular weight (Mw) (based on polystyrene conversion by gel permeation chromatography (GPC)) of the component (A1) is not particularly limited and is preferably from 1,000 to 50,000, more preferably from 1,500 to 30,000, 20000 is more preferable. If it is below the upper limit of the above range, there is a solubility in a resist solvent sufficient for use as a resist. If the lower limit of the above range is exceeded, the dry etching resistance and the cross-sectional shape of the resist pattern are favorable.

The dispersion degree (Mw / Mn) of the component (A1) is not particularly limited, but is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.0 to 2.5. Mn represents the number average molecular weight.

The component (A1) is obtained by copolymerizing a monomer derived from each constituent unit with a known radical using a radical polymerization initiator such as, for example, dimethyl-2,2-azobis (2-methylpropionate) or azobisisobutyronitrile Followed by polymerization or the like.

In addition, (A1) component contains, by using at the time of the polymerization, for example, by combined use of a chain transfer agent such as _{HS-CH 2 -CH 2 -CH 2} -C (CF 3) 2 -OH, -C at the terminal ( CF ₃ ) ₂ -OH group may be introduced. As described above, a copolymer into which a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group is substituted with a fluorine atom is introduced is effective for reduction of defects and reduction of LER (line edge roughness: uneven irregularity of line side wall).

Commercially available monomers for deriving each constituent unit may be used, or those prepared by known methods may be used.

For example, the monomer for deriving the structural unit (a0) is a compound represented by the following general formula (I) (hereinafter referred to as a compound (I)).

The method for producing the compound (I) is not particularly limited, but preferred examples include a method in which a reaction system containing a compound represented by the following general formula (I-1) is added with an alcohol represented by the following general formula (I-2) To obtain a compound (I).

As a specific example of the method for producing the compound (I), for example, by reacting 3-hydroxyadamantan-1-yl acrylate with ClSO ₂ NH ₂ , 3-sulfamoyloxyadamantan- Acrylate can be produced.

(68)

[R, R ^2, R ^3, W in the formula are each the above formula (a0-1) in the R, R ^2, R ^3, equal to the W, and X ^h is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom ]

Examples of the monomer for deriving the structural unit represented by the general formula (a2-0-1) include a compound represented by the following general formula (II) (hereinafter referred to as a compound (II)).

The method for producing the compound (II) is not particularly limited, and can be produced by a known method. For example, a compound (II-2) represented by the following general formula (II-2) is added to a solution in which a compound (II-1) represented by the following general formula (II- Is added and reacted to obtain the compound (II).

Examples of the base include inorganic bases such as sodium hydride, K ₂ CO ₃ and Cs ₂ CO ₃ ; Organic bases such as triethylamine, 4-dimethylaminopyridine (DMAP), and pyridine. Examples of the condensing agent include carbodiimide reagents such as ethyldiisopropylaminocarbodiimide (EDCI) hydrochloride, dicyclohexylcarboxyimide (DCC), diisopropylcarbodiimide and carbodiimidazole, Phosphate, benzotriazole-N-hydroxytrisdimethylaminophosphonium hexafluorophosphate salt (Bop reagent), and the like.

In the above reaction, an acid may be used if necessary. As the acid, those conventionally used for dehydration condensation and the like can be used. Specific examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, and organic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid. For example. These may be used alone or in combination of two or more.

And R < ⁵ > is a lactone-containing cyclic group, can also be produced by the same method.

(69)

[Wherein R, R ⁴ and R ⁵ are the same as R, R ⁴ and R ⁵ in the formula (a2-0-1), respectively]

The structures of the compounds obtained as described above can be measured by ¹ H-nuclear magnetic resonance (NMR) spectroscopy, ¹³ C-NMR spectroscopy, ¹⁹ F-NMR spectroscopy, infrared absorption spectroscopy, mass spectrometry , An elemental analysis method, and an X-ray crystal diffraction method.

In the component (A), as the component (A1), one type may be used alone, or two or more types may be used in combination.

The proportion of the component (A1) in the component (A) is preferably 50% by mass, more preferably 80% by mass or more, and still more preferably 100% by mass with respect to the total mass of the component (A).

The positive resist composition of the present invention comprises a base component (hereinafter, referred to as " component (A2) ") that does not correspond to the component (A1) and has increased solubility in an alkali developer due to the action of an acid ).

(A2) is not particularly limited, and a large number of conventionally known base components for the chemically amplified positive resist composition (for example, for ArF excimer laser, KrF excimer laser (preferably ArF excimer laser (For example, a base resin such as a base resin). For example, examples of the base resin for the ArF excimer laser include a resin having the above-mentioned structural unit (a1) as an essential structural unit and optionally further having the aforementioned structural units (a2) to (a5). Further, it may contain a non-polymer (low molecular weight compound) having a molecular weight of 500 or more and less than 4000.

The component (A2) may be used alone or in combination of two or more.

The content of the component (A) in the positive resist composition of the present invention may be adjusted according to the thickness of the resist film to be formed.

≪ Component (B) >

The component (B) is not particularly limited, and any of those proposed so far as acid generators for chemically amplified resists can be used. Examples of such an acid generator include an onium salt acid generator such as an iodonium salt or a sulfonium salt, an oxime sulfonate acid generator, a bisalkyl or bisaryl sulfonyl diazomethanes, a poly (bis-sulfonyl) diazo Diazomethane-based acid generators such as methanes, nitrobenzylsulfonate-based acid generators, iminosulfonate-based acid generators, and disulfone-based acid generators are known.

As the onium salt-based acid generator, for example, compounds represented by the following general formula (b-1) or (b-2) can be used.

(70)

Wherein R ^{1 "to} R ^3" and R ^{5 "to} R ^6" each independently represents an aryl group or an alkyl group which may have a substituent; Any two of R ^{1 "to} R ^3" in the formula (b-1) may be bonded to each other to form a ring with the sulfur atom in the formula; R ^{4 "represents} an alkyl group, a halogenated alkyl group, an aryl group or an alkenyl group which may have a substituent; R ^1" ~R ^{3 "at} least one of the pieces is an aryl, R ^5" ~R ^{6 "at} least one of the Aryl group]

In formula (b-1), R ^{1 "to} R ^3" each independently represent an aryl group or an alkyl group which may have a substituent. In addition, any two of R ^{1 "to} R ^3" in the formula (b-1) may be bonded to each other to form a ring with the sulfur atom in the formula.

Also, at least one of R ^{1 "to} R ^3" represents an aryl group. Two or more of R ^{1 "~R 3"} is preferably an aryl group and, R ^{1 "~R 3"} of it is most preferable that all of the aryl group.

The aryl group of R ^{1 "to} R ^3" is not particularly limited and includes, for example, an aryl group having 6 to 20 carbon atoms. The aryl group is preferably an aryl group having 6 to 10 carbon atoms in that it can be synthesized at low cost. Specific examples thereof include a phenyl group and a naphthyl group.

The aryl group may have a substituent. The phrase "having a substituent" refers to sense and, as the substituent, an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group, an alkoxy alkyloxy that a part or all of the hydrogen atoms of such an aryl group is substituted with a substituent, -OR ⁵⁰ -C (= O) - (O ) n -R 51 [ wherein, R ⁵⁰ is an alkylene group or a single bond, R ⁵¹ is an acid-cleavable group or sanbi dissociable group, n is 0 or 1], and the like have.

The alkyl group in which the hydrogen atom of the aryl group may be substituted is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.

As the alkoxy group to which the hydrogen atom of the aryl group may be substituted, an alkoxy group having 1 to 5 carbon atoms is preferable, and a methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, Methoxy group and ethoxy group are most preferable.

The halogen atom to which the hydrogen atom of the aryl group may be substituted is preferably a fluorine atom.

Examples of the alkoxyalkyloxy group in which the hydrogen atom of the aryl group may be substituted include -OC (R ⁴⁷ ) (R ⁴⁸ ) -OR ⁴⁹ wherein R ⁴⁷ and R ⁴⁸ are each independently a hydrogen atom or a straight Chain or branched alkyl group, R ⁴⁹ is an alkyl group, and R ⁴⁸ and R ⁴⁹ may be bonded to each other to form a single ring structure. Provided that at least one of R ⁴⁷ and R ⁴⁸ is a hydrogen atom.

In R ⁴⁷ and R ⁴⁸ , the alkyl group has preferably 1 to 5 carbon atoms, more preferably an ethyl group or a methyl group, and most preferably a methyl group.

It is particularly preferable that one of R ⁴⁷ and R ⁴⁸ is a hydrogen atom, the other is a hydrogen atom or a methyl group, and that R ⁴⁷ and R ⁴⁸ are both hydrogen atoms.

The alkyl group for R ⁴⁹ preferably has 1 to 15 carbon atoms, and may be any of linear, branched, and cyclic.

The linear or branched alkyl group for R ⁴⁹ preferably has 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group and a tert-butyl group. .

The cyclic alkyl group for R ⁴⁹ preferably has 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specific examples include monocycloalkane, polycycloalkane such as monocycloalkane, bicycloalkane, tricycloalkane and tetracycloalkane, which may be substituted with an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a fluorinated alkyl group, A group in which a hydrogen atom is removed, and the like. Examples of the monocycloalkane include cyclopentane, cyclohexane, and the like. Examples of the polycycloalkane include adamantane, norbornane, isoborane, tricyclodecane, and tetracyclododecane. Among them, a group obtained by removing at least one hydrogen atom from adamantane is preferable.

R ⁴⁸ and R ⁴⁹ may combine with each other to form a single ring structure. In this case, a cyclic group is formed by the oxygen atom to which R ⁴⁸ and R ⁴⁹ and R ⁴⁹ are bonded and the oxygen atom and the carbon atom to which R ⁴⁸ is bonded. The cyclic group is preferably a 4- to 7-membered ring, and more preferably a 4- to 6-membered ring.

Of the -OR ⁵⁰ -C (= O) - (O) _n -R ⁵¹ wherein the hydrogen atom of the aryl group may be substituted, the alkylene group in R ⁵⁰ is preferably a linear or branched alkylene group , And the carbon number thereof is preferably 1 to 5. [ Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group and a 1,1-dimethylethylene group.

The acid-cleavable group in R ⁵¹ is not particularly limited as long as it is an organic group which can be dissociated by the action of an acid (acid generated from the component (B) upon exposure). For example, Include the same acid-dissociative dissolution inhibiting groups as those exemplified in Examples. Among them, a tertiary alkyl ester type is preferable.

Examples of the acid labile group at R ⁵¹ include a decyl group, a tricyclodecanyl group, an adamantyl group, a 1- (1-adamantyl) methyl group, a tetracyclododecanyl group, an isobornyl group, .

The alkyl group of R ^{1 "} to R ^3" is not particularly limited and includes, for example, a linear, branched or cyclic alkyl group of 1 to 10 carbon atoms. It is preferable that the number of carbon atoms is 1 to 5 in view of excellent resolution. Specific examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, Methyl group is preferable because it is excellent in resolution and can be synthesized at low cost.

The alkyl group may have a substituent. The term " having a substituent (s) " means that a part or all of the hydrogen atoms of the alkyl group are substituted with a substituent. Examples of the substituent include the same ones as those exemplified as substituents of the aryl group.

In formula (b-1), any two of R ^{1 "} to R ^{3" may} be bonded to each other to form a ring with the sulfur atom in the formula. The ring may be saturated or unsaturated. Further, the ring may be a monocycle type or a polycrystalline type. For example, when one or both of the two rings forming the ring is a cyclic group (cyclic alkyl group or aryl group), when they are bonded, a polycyclic ring (condensed ring) is formed.

When two of R ^{1 ''} to R ^{3 ''} are bonded to form a ring, one ring included in the ring skeleton of the sulfur atom in the formula is preferably a 3 to 10-membered ring including a sulfur atom, To 7-membered rings are particularly preferable.

Specific examples of the ring formed by combining two of R ^{1 ''} to R ^{3 ''} include benzothiophene, dibenzothiophene, 9H-thioxanthene, thioxantone, thianthrene, phenoxathine, tetrahydrothiophenium , Tetrahydrothiopyranium, and the like.

When any two of R ^{1 "} to R ^3" are bonded to each other to form a ring together with the sulfur atom in the formula, the remaining one is preferably an aryl group.

When all of R ^{1 "} to R ^3" in the cation portion of the compound represented by the formula (b-1) are a phenyl group which may have a substituent, that is, a preferred specific example in which the cationic portion has a triphenylsulfonium skeleton Include, for example, cation units represented by the following formulas (I-1-1) to (I-1-14).

(71)

Further, it is also preferable that some or all of the phenyl groups in these cation moieties are substituted with naphthyl groups which may have a substituent. Of the three phenyl groups, a naphthyl group is preferably substituted by 1 or 2.

In the case where any two of R ^{1 "} to R ^3" in the cation portion of the compound represented by the formula (b-1) bind to each other to form a ring together with the sulfur atom in the formula, Include cationic moieties represented by the following formulas (I-11-10) to (I-11-13).

(72)

R ⁹ represents a phenyl group which may have a substituent, a naphthyl group which may have a substituent or an alkyl group having a carbon number of 1 to 5, R ¹⁰ represents a phenyl group which may have a substituent, a naphthyl group which may have a substituent, An alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a hydroxyl group, and u is an integer of 1 to 3,

(73)

[Wherein R ⁴¹ to R ⁴⁶ are each independently an alkyl group, an acetyl group, an alkoxy group, a carboxyl group, a hydroxyl group or a hydroxyalkyl group; n ₁ to n ₅ each independently represent an integer of 0 to 3 and n ₆ represents an integer of 0 to 2,

In R ⁹ to R ¹⁰ in the formulas (I-11-10) to (I-11-11), the substituent which the phenyl group or the naphthyl group may have includes an aryl group in R ^{1 "} to R ^3" May be the same as those exemplified as the substituent which may be present. Examples of the substituent which the alkyl group in R ⁹ to R ¹⁰ may have include the same ones as those exemplified as substituents which the alkyl group may have in R ^{1 "} to R ^3" .

u is an integer of 1 to 3, and 1 or 2 is most preferable.

In the formulas (I-11-12) to (I-11-13), in R ⁴¹ to R ⁴⁶ , the alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, and among them, a linear or branched alkyl group And particularly preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group or a tert-butyl group.

The alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a straight-chain or branched-chain alkoxy group, and particularly preferably a methoxy group or an ethoxy group.

The hydroxyalkyl group is preferably a group in which one or more hydrogen atoms of the alkyl group are substituted with a hydroxy group, and examples thereof include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

When the symbols n ₁ to n ₆ assigned to R ⁴¹ to R ⁴⁶ are an integer of 2 or more, a plurality of R ⁴¹ to R ⁴⁶ may be the same or different.

n ₁ is preferably 0 to 2, more preferably 0 or 1, still more preferably 0.

n ₂ and n ₃ are each independently preferably 0 or 1, and more preferably 0.

n ₄ is preferably 0 to 2, more preferably 0 or 1.

n ₅ is preferably 0 or 1, and more preferably 0. [

n ₆ is preferably 0 or 1, and more preferably 1.

In the formulas (b-1) to (b-2), R ^{4 "} represents an alkyl group, a halogenated alkyl group, an aryl group or an alkenyl group which may have a substituent.

The alkyl group in R < ⁴ > may be any of linear, branched and cyclic.

The linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.

The cyclic alkyl group preferably has 4 to 15 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms.

As the halogenated alkyl group for R < ^{4 &} gt ;, there may be mentioned a group in which some or all of the hydrogen atoms of the above-mentioned linear, branched or cyclic alkyl groups are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, , A bromine atom, and an iodine atom, and a fluorine atom is preferable.

In the halogenated alkyl group, the ratio (halogenation ratio (%)) of the number of halogen atoms to the total number of halogen atoms and hydrogen atoms contained in the halogenated alkyl group is preferably 10 to 100%, more preferably 50 to 100% , And most preferably 100%. The higher the halogenation rate is, the more desirable is the strength of the acid.

The aryl group in R < ⁴ > is preferably an aryl group having 6 to 20 carbon atoms.

The alkenyl group in R < ⁴ > is preferably an alkenyl group having 2 to 10 carbon atoms.

In the above-mentioned R ^{4 "} ," may have a substituent "means that some or all of the hydrogen atoms in the above-mentioned linear, branched or cyclic alkyl, halogenated alkyl, aryl or alkenyl group are substituted with a substituent Or other atoms or groups other than hydrogen atoms).

The number of substituents in R ^{4 "} may be one or two or more.

Examples of the substituent include a halogen atom, a hetero atom, an alkyl group, a group represented by the formula: XQ ¹ - wherein Q ¹ is a divalent linking group containing an oxygen atom, and X is a group having 3 to 30 And a group represented by R < 2 >

Examples of the halogen atom and the alkyl group include the same ones exemplified as the halogen atom and the alkyl group in the halogenated alkyl group in R ^{4 "} .

Examples of the heteroatom include an oxygen atom, a nitrogen atom, and a sulfur atom.

In the group represented by XQ ¹ -, Q ¹ is a divalent linking group containing an oxygen atom.

Q ¹ may contain an atom other than an oxygen atom. Examples of the atom other than the oxygen atom include a carbon atom, a hydrogen atom, a sulfur atom, and a nitrogen atom.

Examples of the divalent linking group containing an oxygen atom include an oxygen atom (ether bond; -O-), an ester bond (-C (= O) -O-), an amide bond (-C -NH-), a carbonyl group (-C (= O) -), a carbonate bond (-OC (= O) -O-) and the like; A combination of a non-hydrocarbon-based oxygen atom-containing linking group and an alkylene group, and the like.

Examples of such combinations include -R ⁹¹ -O-, -R ⁹² -OC (= O) -, -C (= O) -OR ⁹³ -, -C (= O) -OR ⁹³ -OC = O) - (wherein R ⁹¹ to R ⁹³ each independently represents an alkylene group).

The alkylene group in R ⁹¹ to R ⁹³ is preferably a linear or branched alkylene group, and the alkylene group of the alkylene group is preferably from 1 to 12, more preferably from 1 to 5, 3 is particularly preferable.

Specific examples of the alkylene group include a methylene group [-CH ₂ -]; _{-CH (CH 3) -, -CH} (CH 2 CH 3) -, -C (CH 3) 2 -, -C (CH 3) (CH 2 CH 3) -, -C (CH 3) (CH 2 CH ₂ CH ₃ ) -, -C (CH ₂ CH ₃ ) ₂ -; Ethylene group [-CH ₂ CH ₂ -]; _{-CH (CH 3) CH 2 -} , -CH (CH 3) CH (CH 3) -, -C (CH 3) 2 CH 2 -, -CH (CH 2 CH 3) CH 2 -, -CH (CH ₂ CH ₃ ) CH ₂ -; A trimethylene group (n-propylene group) [-CH ₂ CH ₂ CH ₂ -]; _{-CH (CH 3) CH 2 CH} 2 -, -CH 2 CH (CH 3) CH 2 - alkyl trimethylene group and the like; A tetramethylene group [-CH ₂ CH ₂ CH ₂ CH ₂ -]; An alkyltetramethylene group such as -CH (CH ₃ ) CH ₂ CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) CH ₂ CH ₂ -; A pentamethylene group [-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -] and the like.

As Q ¹ , a divalent linking group containing an ester bond or an ether bond is preferable, and among them, -R ⁹¹ -O-, -R ⁹² -OC (= O) -, -C (= O) C (= O) -OR ⁹³ - or -C (= O) -OR ⁹³ -OC (= O) -.

In the group represented by XQ ¹ -, the hydrocarbon group of X may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.

The aromatic hydrocarbon group is a hydrocarbon group having an aromatic ring. The number of carbon atoms of the aromatic hydrocarbon group is preferably from 3 to 30, more preferably from 5 to 30, still more preferably from 5 to 20, particularly preferably from 6 to 15, most preferably from 6 to 12. Provided that the number of carbon atoms does not include the number of carbon atoms in the substituent.

Specific examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group and a phenanthryl group, And an arylalkyl group such as a substituted or unsubstituted aryl group, a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group and a 2-naphthylethyl group. The number of carbon atoms of the alkyl chain in the arylalkyl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

The aromatic hydrocarbon group may have a substituent. For example, some of the carbon atoms constituting the aromatic ring of the aromatic hydrocarbon group may be substituted by a hetero atom, and the hydrogen atoms bonded to the aromatic ring of the aromatic hydrocarbon group may be substituted by a substituent.

Examples of the former include a heteroaryl group in which a part of the carbon atoms constituting the ring of the aryl group is substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, a part of carbon atoms constituting the aromatic hydrocarbon ring in the arylalkyl group Is a heteroarylalkyl group substituted by the above-mentioned hetero atom.

Examples of the substituent of the aromatic hydrocarbon group in the latter examples include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group and an oxygen atom (= O).

The alkyl group as a substituent of the aromatic hydrocarbon group is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.

The alkoxy group as a substituent of the aromatic hydrocarbon group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, And a methoxy group and an ethoxy group are most preferable.

Examples of the halogen atom as a substituent of the aromatic hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

Examples of the halogenated alkyl group as a substituent of the aromatic hydrocarbon group include groups in which a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom.

The aliphatic hydrocarbon group in X may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be any of linear, branched, and cyclic.

In the formula (X), the aliphatic hydrocarbon group may be substituted with a substituent group in which a part of the carbon atoms constituting the aliphatic hydrocarbon group is substituted with a hetero atom, and a part or all of the hydrogen atoms constituting the aliphatic hydrocarbon group may be substituted with a substituent containing a hetero atom Or may be substituted.

The "hetero atom" in X is not particularly limited as far as it is an atom other than a carbon atom and a hydrogen atom, and examples thereof include a halogen atom, an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, an iodine atom and a bromine atom.

The "substituent group containing a hetero atom" (hereinafter sometimes referred to as a hetero atom-containing substituent) may be composed of only the above-mentioned hetero atom, or may be a group containing a group or an atom other than the above-mentioned hetero atom.

Examples of the heteroatom-containing substituent which may partially replace the carbon atoms constituting the aliphatic hydrocarbon group include -O-, -C (= O) -O-, -C (= O) -, -OC O) -O-, -C (= O ) -NH-, -NH- ( H or may have been substituted with a substituent such as an alkyl group, an acyl group), -S-, -S (= O ) 2 -, - S (= O) _2- O-, and the like. (Alkyl group, acyl group, etc.) to which H may be substituted preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, particularly preferably 1 to 5 carbon atoms Do.

When the aliphatic hydrocarbon group is cyclic, these substituents may be contained in the ring structure.

A heteroatom-containing substituent may be substituted for part or all of the hydrogen atoms constituting the aliphatic hydrocarbon group include, for example, a halogen atom, an alkoxy group, a hydroxyl ^{group, -C (= O) -R 80} [R 80 is an alkyl group ], -COOR ⁸¹ [R ⁸¹ is a hydrogen atom or an alkyl group, a halogenated alkyl group, halogenated alkoxy group, an amino group, an amide group, a nitro group, an oxygen atom (= O), a sulfur atom, a sulfonyl group (SO _2), etc. .

Examples of the halogen atom as the hetero atom-containing substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

The alkyl group in the alkoxy group as the hetero atom-containing substituent may be any of linear, branched, and cyclic alkyl groups and may be a combination thereof. The carbon number thereof is preferably from 1 to 30. When the alkyl group is a linear or branched chain, the number of carbon atoms thereof is preferably from 1 to 20, more preferably from 1 to 17, still more preferably from 1 to 15, and particularly preferably from 1 to 10. Specifically, the same examples as the specific examples of the linear or branched saturated hydrocarbon group exemplified below can be mentioned. When the alkyl group is cyclic (when it is a cycloalkyl group), the number of carbon atoms thereof is preferably from 3 to 30, more preferably from 3 to 20, still more preferably from 3 to 15, particularly preferably from 4 to 12 , Most preferably from 5 to 10 carbon atoms. The alkyl group may be monocyclic or polycyclic. Specific examples thereof include groups obtained by removing one or more hydrogen atoms from a monocycloalkane, groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as bicycloalkane, tricycloalkane and tetracycloalkane, and the like. Specific examples of the monocycloalkane include cyclopentane, cyclohexane, and the like. Specific examples of the polycycloalkane include adamantane, norbornane, isoborane, tricyclodecane, tetracyclododecane, and the like. In these cycloalkyl groups, a part or all of the hydrogen atoms bonded to the ring may be substituted with a substituent such as a fluorine atom or a fluorinated alkyl group, or may not be substituted.

In the -C (= O) -R ⁸⁰ and -COOR ⁸¹ as the hetero atom-containing substituent, examples of the alkyl group in R ⁸⁰ and R ⁸¹ include the same alkyl groups exemplified as the alkyl groups in the alkoxy group .

Examples of the alkyl group in the halogenated alkyl group as the hetero atom-containing substituent include the same alkyl groups exemplified as the alkyl group in the alkoxy group. As the halogenated alkyl group, a fluorinated alkyl group is particularly preferable.

Examples of the halogenated alkoxy group as the hetero atom-containing substituent include groups in which a part or all of the hydrogen atoms of the alkoxy group are substituted with the halogen atom. As the halogenated alkoxy group, a fluorinated alkoxy group is preferable.

Examples of the hydroxyalkyl group as the hetero atom-containing substituent include groups in which at least one hydrogen atom of the alkyl group exemplified as the alkyl group in the alkoxy group is substituted with a hydroxyl group. The number of hydroxyl groups contained in the hydroxyalkyl group is preferably 1 to 3, and most preferably 1.

The aliphatic hydrocarbon group is preferably a linear or branched saturated hydrocarbon group, a linear or branched monovalent unsaturated hydrocarbon group, or a cyclic aliphatic hydrocarbon group (aliphatic cyclic group).

The linear saturated hydrocarbon group (alkyl group) preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, , A tetradecyl group, a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a heneicosyl group, and a docosyl group.

The branched-chain saturated hydrocarbon group (alkyl group) preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specific examples thereof include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, Ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group and 4-methylpentyl group.

The unsaturated hydrocarbon group preferably has 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms, more preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. Examples of the linear monovalent unsaturated hydrocarbon group include a vinyl group, a propenyl group (allyl group), and a butyryl group. Examples of the branched monovalent unsaturated hydrocarbon group include a 1-methylpropenyl group and a 2-methylpropenyl group. As the unsaturated hydrocarbon group, a propenyl group is particularly preferable.

The aliphatic cyclic group may be a monocyclic group or a polycyclic group. The number of carbon atoms is preferably from 3 to 30, more preferably from 5 to 30, still more preferably from 5 to 20, particularly preferably from 6 to 15, most preferably from 6 to 12.

Specifically, for example, groups in which one or more hydrogen atoms have been removed from a monocycloalkane; And groups obtained by removing one or more hydrogen atoms from a polycycloalkane such as a bicycloalkane, tricycloalkane, or tetracycloalkane. More specifically, groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane, cyclohexane and the like; And groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, norbornane, isoborane, tricyclodecane, and tetracyclododecane.

When the aliphatic cyclic group does not contain a substituent group containing a heteroatom in the ring structure, the aliphatic cyclic group is preferably a polycyclic group, more preferably a group in which at least one hydrogen atom is removed from the polycycloalkane, Most preferably a group in which at least one hydrogen atom has been removed.

When the aliphatic cyclic group contains a substituent group containing a heteroatom in the ring structure, the substituent group containing the heteroatom includes -O-, -C (= O) -O-, -S-, S (= O) ₂ -, -S (= O) ₂ -O-. Specific examples of such an aliphatic cyclic group include groups represented by the following formulas (L1) to (L5), (S1) to (S4), and the like.

≪ EMI ID =

Wherein Q "is an alkylene group, an oxygen atom or a sulfur atom which may contain an oxygen atom or a sulfur atom, and m is an integer of 0 or 1,

The alkylene group in Q "is preferably a linear or branched chain, and the number of carbon atoms thereof is preferably from 1 to 5. Specific examples thereof include a methylene group [-CH ₂ -], -CH (CH ₃ -, -CH (CH ₂ CH ₃ ) -, -C (CH ₃ ) ₂ -, -C (CH ₃ ) (CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₂ CH ₃ ) _{-, -C (CH 2 CH 3} ) 2 - a methylene group of the alkyl and the like; an ethylene group _{[-CH 2 CH 2 -];} -CH (CH 3) CH 2 -, -CH (CH 3) CH (CH 3) -, an alkylethylene group such as -C (CH ₃ ) ₂ CH ₂ -, -CH (CH ₂ CH ₃ ) CH ₂ -, a trimethylene group (n-propylene group) [-CH ₂ CH ₂ CH ₂ -]; _{-CH (CH 3) CH 2 CH} 2 -, -CH 2 CH (CH 3) CH 2 - alkyl trimethylene group and the like; a tetramethylene group _{[-CH 2 CH 2 CH 2 CH} 2 -]; -CH (CH ₃ ) an alkyltetramethylene group such as CH ₂ CH ₂ CH ₂ -, -CH ₂ CH (CH ₃ ) CH ₂ CH ₂ -, a pentamethylene group [-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ - Among them, a methylene group or an alkylmethylene group is preferable, and a methylene group, -CH (CH ₃ ) - or -C (CH ₃ ) ₂ - is particularly preferable.

The alkylene group may contain an oxygen atom (-O-) or a sulfur atom (-S-). Specific examples thereof include a group in which -O- or -S- is interposed between the terminal or carbon atom of the alkylene group, for example, -OR ⁹⁴ -, -SR ⁹⁵ -, -R ⁹⁶ -OR ⁹⁷ -, -R ⁹⁸ -SR ⁹⁹ -, and the like. Here, R ⁹⁴ to R ⁹⁹ each independently represents an alkylene group. Examples of the alkylene group include the same alkylene groups as exemplified as the alkylene group in the above Q ". Among them, -O-CH ₂ -, -CH ₂ -O-CH ₂ -, -S-CH ₂ -, -CH ₂ -S-CH ₂ -, and the like.

In these aliphatic cyclic groups, a part or all of the hydrogen atoms may be substituted with a substituent. Examples of the substituent include an alkyl group, a halogen atom, an alkoxy group, a hydroxyl group, -C (= O) -R ⁸⁰ (R ⁸⁰ is an alkyl group), -COOR ⁸¹ (R ⁸¹ is a hydrogen atom or an alkyl group) A halogenated alkyl group, a halogenated alkoxy group, an amino group, an amide group, a nitro group, an oxygen atom (= O), a sulfur atom and a sulfonyl group (SO ₂ ).

Examples of the alkyl group as the substituent include the same ones exemplified as the alkyl group in the above-mentioned alkoxy group as the hetero atom-containing substituent.

The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably a linear or branched chain and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, Pentyl group, neopentyl group, hexyl group and the like. Among them, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

The halogen atom, the alkoxy group, -C (= O) -R ⁸⁰ , -COOR ⁸¹ , the halogenated alkyl group and the halogenated alkoxy group as the substituent may be the same or different and each represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group, Containing substituent can be exemplified.

As the substituent substituting the hydrogen atom of the aliphatic cyclic group, an alkyl group, an oxygen atom (= O) and a hydroxyl group are preferable.

The number of substituents of the aliphatic cyclic group may be one or two or more. When a plurality of substituents are present, the plurality of substituents may be the same or different.

X is preferably a cyclic group which may have a substituent. The cyclic group may be an aromatic hydrocarbon group which may have a substituent, an aliphatic cyclic group which may have a substituent or an aliphatic cyclic group which may have a substituent.

The aromatic hydrocarbon group is preferably a naphthyl group which may have a substituent or a phenyl group which may have a substituent.

The aliphatic cyclic group which may have a substituent is preferably a polycyclic aliphatic cyclic group which may have a substituent. Examples of the polycyclic aliphatic cyclic group include groups in which at least one hydrogen atom has been removed from the polycycloalkane, groups represented by the above-mentioned (L2) to (L5), (S3) to (S4).

In the present invention, R ^{4 "is} a substituent ¹ XQ - it is desirable to have this case, R ^4." Roneun XQ ¹ -Y ¹ - [wherein, Q ¹ and X are as defined above and, Y ¹ is An alkylene group having 1 to 4 carbon atoms which may have a substituent, or a fluorinated alkylene group having 1 to 4 carbon atoms which may have a substituent].

In the group represented by XQ ¹ -Y ¹ -, examples of the alkylene group for Y ¹ include the same alkylene groups as those having 1 to 4 carbon atoms in the alkylene group exemplified for Q ¹ above.

The fluorinated alkylene group includes a group in which a part or all of the hydrogen atoms of the alkylene group are substituted with a fluorine atom.

Specific examples of Y ¹ include -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, -CF (CF ₃ ) CF ₂ -, -CF (CF ₂ CF ₃ ) -, -C _{(CF 3) 2-, -CF 2} CF 2 CF 2 CF 2 -, -CF (CF 3) CF 2 CF 2 -, -CF 2 CF (CF 3) CF 2 -, -CF (CF 3) CF ( _{CF 3) -, -C (CF} 3) 2 CF 2 -, -CF (CF 2 CF 3) CF 2 -, -CF (CF 2 CF 2 CF 3) -, -C (CF 3) (CF 2 CF ₃ ) -; _{-CHF-, -CH 2 CF 2 -,} -CH 2 CH 2 CF 2 -, -CH 2 CF 2 CF 2 -, -CH (CF 3) CH 2 -, -CH (CF 2 CF 3) -, - _{C (CH 3) (CF 3} ) -, -CH 2 CH 2 CH 2 CF 2 -, -CH 2 CH 2 CF 2 CF 2 -, -CH (CF 3) CH 2 CH 2 -, -CH 2 CH ( _{CF 3) CH 2 -, -CH} (CF 3) CH (CF 3) -, -C (CF 3) 2 CH 2 -; _{-CH 2 -, -CH 2 CH 2} -, -CH 2 CH 2 CH 2 -, -CH (CH 3) CH 2 -, -CH (CH 2 CH 3) -, -C (CH 3) 2 -, _{-CH 2 CH 2 CH 2 CH 2} -, -CH (CH 3) CH 2 CH 2 -, -CH 2 CH (CH 3) CH 2 -, -CH (CH 3) CH (CH 3) -, -C (CH ₃ ) ₂ CH ₂ -, -CH (CH ₂ CH ₃ ) CH ₂ -, -CH (CH ₂ CH ₂ CH ₃ ) -, -C (CH ₃ ) (CH ₂ CH ₃ ) have.

Y ¹ is preferably a fluorinated alkylene group, particularly preferably a fluorinated alkylene group in which a carbon atom bonded to an adjacent sulfur atom is fluorinated. Examples of such fluorinated alkylene groups include -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ -, -CF (CF ₃ ) CF ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ -, - _{CF (CF 3) CF 2 CF} 2 -, -CF 2 CF (CF 3) CF 2 -, -CF (CF 3) CF (CF 3) -, -C (CF 3) 2 CF 2 -, -CF ( _{CF 2 CF 3) CF 2 -} ; -CH ₂ CF ₂ -, -CH ₂ CH ₂ CF ₂ -, -CH ₂ CF ₂ CF ₂ -; -CH ₂ CH ₂ CH ₂ CF ₂ -, -CH ₂ CH ₂ CF ₂ CF ₂ -, -CH ₂ CF ₂ CF ₂ CF ₂ - and the like.

Among them, -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ - or -CH ₂ CF ₂ CF ₂ - are preferable, and -CF ₂ -, -CF ₂ CF ₂ - or -CF ₂ CF ₂ CF ₂ - is more preferable, and -CF ₂ - is particularly preferable.

The alkylene group or the fluorinated alkylene group may have a substituent. "An alkylene group or a fluorinated alkylene group" having a substituent "means that a part or all of a hydrogen atom or a fluorine atom in the alkylene group or the fluorinated alkylene group is substituted with an atom or group other than a hydrogen atom and a fluorine atom .

Examples of the substituent which the alkylene group or the fluorinated alkylene group may have include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, and the like.

In the formula (b-2), R ^{5 "} to R ^6" each independently represent an aryl group or an alkyl group. At least one of R ^{5 "} to R ^6" represents an aryl group. It is preferable that all of R ^" to R ^" are aryl groups.

The aryl group of R ^{5 "} to R ^{6" includes} the same aryl groups as R ^{1 "} to R ^3" .

Examples of the alkyl group represented by R ^{5 "} to R ^{6" include} the same alkyl groups as those represented by R ^{1 "} to R ^3" .

Among them, it is most preferable that R ^{5 "} to R ^6" are all phenyl groups.

Formula (b-2) of R ⁴ are the same as the ^"roneun R ⁴ in the formula ^(b-1)".

Specific examples of onium salt-based acid generators represented by the formulas (b-1) and (b-2) include trifluoromethanesulfonate or nonafluorobutanesulfonate of diphenyliodonium; Trifluoromethanesulfonate or nonafluorobutanesulfonate of bis (4-tert-butylphenyl) iodonium; Trifluoromethanesulfonate of triphenylsulfonium, heptafluoropropanesulfonate thereof or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of tri (4-methylphenyl) sulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of dimethyl (4-hydroxynaphthyl) sulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of monophenyldimethylsulfonium, heptafluoropropanesulfonate thereof or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of diphenyl monomethylsulfonium, heptafluoropropanesulfonate thereof or nonafluorobutanesulfonate thereof; (4-methylphenyl) diphenylsulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Tri (4-tert-butyl) phenylsulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of diphenyl (1- (4-methoxy) naphthyl) sulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of di (1-naphthyl) phenylsulfonium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1-phenyltetrahydrothiophenium, heptafluoropropanesulfonate thereof or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-methylphenyl) tetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-ethoxynaphthalen-1-yl) tetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1-phenyltetrahydrothiopyranium, heptafluoropropanesulfonate thereof or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-hydroxyphenyl) tetrahydrothiopyranium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiopyran, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof; Trifluoromethanesulfonate of 1- (4-methylphenyl) tetrahydrothiopyranium, heptafluoropropanesulfonate or nonafluorobutanesulfonate thereof, and the like.

Also, the anion of these onium salts can be reacted with methanesulfonate, n-propanesulfonate, n-butanesulfonate, n-octanesulfonate, 1-adamantanesulfonate, 2-norbornanesulfonate, Alkylsulfonates which may have a substituent, such as 10-sulfonate; Or an onium salt substituted with an aromatic sulfonate such as benzenesulfonate, perfluorobenzenesulfonate or p-toluenesulfonate can also be used.

An onium salt substituted with an anion represented by any one of the following formulas (b1) to (b8) can also be used.

(75)

Wherein p is an integer of 1 to 3, v 0 is an integer of 0 to 3, q 1 to q 2 are each independently an integer of 1 to 5, q 3 is an integer of 1 to 12, and r 1 to r 2 are Independently, an integer of 0 to 3, g is an integer of 1 to 20, t 3 is an integer of 1 to 3, R ⁷ is a substituent and R ⁸ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, Lt; / RTI >

[Formula 76]

Wherein, p, R ^7, Q "are each the same and, n1 ~ n5 are each independently 0 or 1, v1 ~ v5 each independently represents an integer of 0 ~ 3, w1 ~ w5 each independently Is an integer of 0 to 3]

Examples of the substituent for R ⁷ include an alkyl group and a heteroatom-containing substituent. Examples of the alkyl group include the same alkyl groups exemplified as substituents which the aromatic hydrocarbon group may have in the description of X above. Examples of the heteroatom-containing substituent include the same ones exemplified as the heteroatom-containing substituent which may be substituted for part or all of the hydrogen atoms constituting the aliphatic hydrocarbon group in the description of X.

R ^7, if a code (~ r2 r1, w1 ~ w5) the integer equal to or greater than two, the plurality of R ⁷ in the compound may be the same, respectively, or different to give.

Examples of the alkyl group and halogenated alkyl group in R ⁸ include the same alkyl groups and halogenated alkyl groups as those in R above.

Each of r1 to r2 and w1 to w5 is preferably an integer of 0 to 2, more preferably 0 or 1.

v0 to v5 are preferably 0 to 2, and most preferably 0 or 1.

t3 is preferably 1 or 2, and most preferably 1.

q3 is preferably 1 to 5, more preferably 1 to 3, most preferably 1.

Examples of the onium salt-based acid generators include those in which the anion moiety in the general formula (b-1) or (b-2) is substituted with an anion represented by the following general formula (b-3) An onium salt acid generation system can be used (the cation unit is the same as (b-1) or (b-2)).

[Formula 77]

Wherein X "represents an alkylene group having 2 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; Y" and Z "each independently represent an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom Lt; / RTI &

X "is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms of the alkylene group is 2 to 6, preferably 3 to 5, and most preferably 3 .

Y "and Z" are independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, Has 1 to 3 carbon atoms.

The smaller the number of carbon atoms of the alkylene group of X "or the number of carbon atoms of the alkyl group of Z" within the above-mentioned carbon number range, the better the solubility in a resist solvent, etc.

The higher the number of hydrogen atoms substituted with fluorine atoms in the alkylene group of X "or the alkyl group of Y" and Z ", the higher the strength of the acid and the higher the transparency to high energy light of 200 nm or less and the electron beam The proportion of the fluorine atom in the alkylene group or alkyl group, that is, the fluorine atom-containing ratio, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably, all hydrogen atoms are substituted with fluorine atoms A perfluoroalkylene group or a perfluoroalkyl group.

In the general formula (b-1) or (b-2), the anion moiety (R ^{4 "} SO ₃ -) may be replaced by R ^7" -COO- wherein R ^{7 "} is an alkyl group or a fluorinated alkyl group ] (The cation unit is the same as (b-1) or (b-2)).

R ^{7 "} includes the same ones as those described above for R ^4" .

Specific examples of the above "R ^7" -COO- include trifluoroacetic acid ion, acetic acid ion, 1-adamantanecarboxylic acid ion, and the like.

In the present specification, the oxime sulfonate-based acid generator is a compound having at least one group represented by the following general formula (B-1) and has a property of generating an acid upon irradiation with radiation. Since such oxime sulfonate-based acid generators are widely used for chemically amplified resist compositions, they can be arbitrarily selected and used.

(78)

(In the formula (B-1), R ³¹ and R ³² each independently represent an organic group)

The organic group of R ³¹ and R ³² is a group containing a carbon atom and is an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (fluorine atom, chlorine atom, etc.) .

The organic group represented by R ³¹ is preferably an alkyl group or aryl group of a linear, branched, or cyclic type. These alkyl group and aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include a fluorine atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, and the like. Here, the term "having a substituent" means that a part or all of the hydrogen atoms of the alkyl group or the aryl group is substituted with a substituent.

The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms, most preferably 1 to 4 carbon atoms. As the alkyl group, particularly a partially or fully halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is preferable. The partially halogenated alkyl group means an alkyl group in which a part of the hydrogen atoms are substituted with halogen atoms and the fully halogenated alkyl group means an alkyl group in which all of the hydrogen atoms are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.

The aryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms. As the aryl group, a partially or fully halogenated aryl group is particularly preferred. Further, the partially halogenated aryl group means an aryl group in which a part of the hydrogen atoms are substituted with halogen atoms, and the completely halogenated aryl group means an aryl group in which all of the hydrogen atoms are substituted with halogen atoms.

R ³¹ is preferably an alkyl group having 1 to 4 carbon atoms or a fluorinated alkyl group having 1 to 4 carbon atoms, which has no substituent.

As the organic group for R ³² , an alkyl group, an aryl group or a cyano group is preferably a linear, branched or cyclic alkyl group. Examples of the alkyl group and aryl group for R ^{32 include} the same alkyl groups and aryl groups exemplified for R ³¹ above.

As R ³² , a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms is particularly preferable.

More preferable examples of the oxime sulfonate-based acid generator include compounds represented by the following general formula (B-2) or (B-3).

(79)

[In the formula (B-2), R ³³ is a cyano group, an alkyl group having no substituent or a halogenated alkyl group. R ³⁴ is an aryl group. And R ³⁵ is an alkyl group having no substituent or a halogenated alkyl group]

(80)

[In the formula (B-3), R ³⁶ is a cyano group, an alkyl group having no substituent or a halogenated alkyl group. R ³⁷ is a bivalent or trivalent aromatic hydrocarbon group. R ³⁸ is an alkyl group having no substituent or a halogenated alkyl group. p "is 2 or 3]

In the general formula (B-2), the alkyl group or halogenated alkyl group having no substituent represented by R ³³ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms .

As R ³³ , a halogenated alkyl group is preferable, and a fluorinated alkyl group is more preferable.

The fluorinated alkyl group for R ³³ preferably has 50% or more of the hydrogen atoms of the alkyl group fluorinated, more preferably 70% or more fluorinated, and particularly preferably 90% or more fluorinated.

Examples of the aryl group for R ³⁴ include an aromatic hydrocarbon ring such as a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthryl group, And a heteroaryl group in which a part of the carbon atoms constituting the ring of these groups is substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. Among them, a fluorenyl group is preferable.

The aryl group of R ³⁴ may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, or an alkoxy group. The alkyl group or halogenated alkyl group in this substituent preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. The halogenated alkyl group is preferably a fluorinated alkyl group.

The alkyl group or halogenated alkyl group having no substituent represented by R ³⁵ preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms.

As R ³⁵ , a halogenated alkyl group is preferable, and a fluorinated alkyl group is more preferable.

The fluorinated alkyl group for R < ³⁵ > preferably has 50% or more of the hydrogen atoms of the alkyl group fluorinated, more preferably 70% or more fluorinated, more preferably 90% or more fluorinated, Do. Most preferably a fully fluorinated alkyl group in which the hydrogen atom is 100% fluorine-substituted.

In the general formula (B-3), examples of the alkyl group having no substituent or the halogenated alkyl group for R ^{36 include} the same alkyl group or halogenated alkyl group having no substituent for R ³³ .

Examples of the divalent or trivalent aromatic hydrocarbon group for R ³⁷ include groups in which one or two hydrogen atoms have been further removed from the aryl group for R ³⁴ .

Examples of the alkyl group having no substituent or the halogenated alkyl group for R ^{38 include} the same alkyl group or halogenated alkyl group having no substituent for R ^{35 described} above.

p "is preferably 2.

Specific examples of the oxime sulfonate-based acid generators include α- (p-toluenesulfonyloxyimino) -benzyl cyanide, α- (p-chlorobenzenesulfonyloxyimino) -benzyl cyanide, α- (4-nitrobenzenesulfonyloxyimino) -benzylcyanide,? - (4-nitro-2-trifluoromethylbenzenesulfonyloxyimino) (Benzenesulfonyloxyimino) -2,4-dichlorobenzyl cyanide,? - (benzenesulfonyloxyimino) -2,6-dichlorobenzyl cyanide,? - (benzenesulfonyloxyimino) (2-chlorobenzenesulfonyloxyimino) -4-methoxybenzyl cyanide,? - (benzenesulfonyloxyimino) -thien-2-yl acetonitrile, [alpha] - (4-dodecylbenzenesulfonyloxyimino) -benzyl cyanide, [alpha] - [(p- toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, alpha - [(dodecylbenzenesulfonyloxy) Amino) -4- (Methylsulfonyloxyimino) -1-cyclopentenyl acetonitrile,? - (methylsulfonyloxyimino) -1-cyclopentenylsuccinonitrile, -Cyclohexenyl acetonitrile,? - (methylsulfonyloxyimino) -1-cycloheptenyl acetonitrile,? - (methylsulfonyloxyimino) -1-cyclooctenyl acetonitrile,? - (trifluoromethyl (Trifluoromethylsulfonyloxyimino) -cyclohexyl acetonitrile,? - (ethylsulfonyloxyimino) -ethylacetonitrile,? - (propylsulfonyloxyimino) (Cyclohexylsulfonyloxyimino) -cyclopentyl acetonitrile,? - (cyclohexylsulfonyloxyimino) -cyclohexyl acetonitrile,? - (cyclohexylsulfonyloxyimino) Amino) -1-cyclopentenyl acetonitrile, a- (ethylsulfonyloxyimino) -1-cyclopentane (Isopropylsulfonyloxyimino) -1-cyclopentenyl acetonitrile,? - (n-butylsulfonyloxyimino) -1-cyclopentenyl acetonitrile,? - (ethylsulfonyloxyimino) (Isopropylsulfonyloxyimino) -1-cyclohexenyl acetonitrile,? - (n-butylsulfonyloxyimino) -1-cyclohexenyl acetonitrile, ? - (methylsulfonyloxyimino) -phenylacetonitrile,? - (methylsulfonyloxyimino) -p-methoxyphenylacetonitrile,? - (trifluoromethylsulfonyloxyimino) -phenylacetonitrile,? - (trifluoromethylsulfonyloxyimino) -p-methoxyphenylacetonitrile,? - (ethylsulfonyloxyimino) -p-methoxyphenylacetonitrile,? - (propylsulfonyloxyimino) -p- Methylphenylacetonitrile,? - (methylsulfonyloxyimino) -p-bromophenylacetonitrile, and the like.

Further, oxime sulfonate-based acid generators disclosed in Japanese Patent Application Laid-Open No. 9-208554 (paragraphs [0012] to [0014], [Chemical formulas 18] to [Chemical formula 19]), WO 2004/074242A2 The oximesulfonate-based acid generators disclosed in Examples 1-40 on page 85 can be used advantageously.

Preferred examples include the following.

[Formula 81]

[0035] Specific examples of the bisalkyl or bisaryl sulfonyl diazomethanes among the diazomethane acid generators include bis (isopropylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane and the like.

The diazomethane-based acid generating system disclosed in JP-A-11-035551, JP-A-11-035552, and JP-A-11-035573 can be preferably used.

Examples of the poly (bis-sulfonyl) diazomethanes include 1,3-bis (phenylsulfonyldiazomethylsulfonyl) propane, 1, 2-bis (Phenylsulfonyldiazomethylsulfonyl) butane, 1,6-bis (phenylsulfonyldiazomethylsulfonyl) hexane, 1,10-bis (phenylsulfonyldiazomethylsulfonyl) Bis (cyclohexylsulfonyldiazomethylsulfonyl) ethane, 1,3-bis (cyclohexylsulfonyldiazomethylsulfonyl) propane, 1,6-bis (cyclohexylsulfonyldiazomethylsulfonyl) Hexylsulfonyl) hexane, and 1,10-bis (cyclohexylsulfonyldiazomethylsulfonyl) decane.

As the component (B), these acid generators may be used singly or in combination of two or more.

In the present invention, as the component (B), it is preferable to use an onium salt-based acid generator in which a fluorinated alkylsulfonic acid ion is anion.

The content of the component (B) in the resist composition of the present invention is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, per 100 parts by mass of the component (A). By setting the thickness to the above range, sufficient pattern formation can be achieved. In addition, a homogeneous solution can be obtained and storage stability is improved, which is preferable.

<Optional ingredients>

The positive resist composition of the present invention may contain a nitrogen-containing organic compound (D) (hereinafter referred to as a component (D)) as an optional component.

The component (D) is not particularly limited as long as it acts as an acid diffusion control agent, that is, as a quencher trapping an acid generated from the component (B) by exposure. You can use it arbitrarily.

As the component (D), a low-molecular compound (non-polymeric) is usually used. Examples of the component (D) include amines such as aliphatic amines and aromatic amines, aliphatic amines are preferable, and secondary aliphatic amines and tertiary aliphatic amines are particularly preferable. Here, the aliphatic amine is an amine having at least one aliphatic group, and the aliphatic group preferably has 1 to 20 carbon atoms.

As the aliphatic amine, for example, at least one of the hydrogen atoms of ammonia (NH ₃ ) may be substituted with an alkyl (alkylamine or alkyl alcohol amine) substituted with an alkyl group or a hydroxyalkyl group having 20 or less carbon atoms or a cyclic amine .

Specific examples of alkyl amines and alkyl alcohol amines include monoalkyl amines such as n-hexyl amine, n-heptyl amine, n-octyl amine, n-nonyl amine, and n-decyl amine; Dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine and dicyclohexylamine; N-hexylamine, tri-n-pentylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-pentylamine, tri- trialkylamines such as n-nonylamine, tri-n-decylamine and tri-n-dodecylamine; Alkyl alcohol amines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine, stearyldiethanolamine and lauryldiethanolamine have. Of these, trialkylamines and / or alkyl alcohol amines are preferred.

The cyclic amine includes, for example, heterocyclic compounds containing a nitrogen atom as a hetero atom. The heterocyclic compound may be monocyclic (aliphatic monocyclic amine) or polycyclic (aliphatic polycyclic amine).

Specific examples of the aliphatic monocyclic amine include piperidine, piperazine, and the like.

As the aliphatic polycyclic amines, the number of carbon atoms is preferably from 6 to 10. Specific examples thereof include 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, hexamethylenetetramine, 1,4-diazabicyclo [2.2.2] octane, and the like.

Other aliphatic amines include tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl } Amine, tris {2- (1-ethoxypropoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} , Tris [2- {2- (2-hydroxyethoxy) ethoxy} ethylamine, and the like.

Examples of the aromatic amine include aniline, pyridine, 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, diphenylamine, triphenylamine, tribenzylamine, 2,6-di Isopropyl aniline, 2,2'-dipyridyl, 4,4'-dipyridyl, and the like.

These may be used alone or in combination of two or more.

The component (D) is usually used in a range of 0.01 to 5.0 parts by mass based on 100 parts by mass of the component (A). By setting the resistivity to the above range, the resist pattern shape, time-course stability after exposure, and the like are improved.

The positive resist composition of the present invention may contain, as optional components, an organic carboxylic acid, and an organic acid such as an oxo acid of phosphorus and an oxo acid of phosphorus and a derivative thereof, in order to prevent deterioration of sensitivity, shape of resist pattern, (Hereinafter, referred to as component (E)) selected from the group consisting of the compounds (A) and (B).

As the organic carboxylic acid, for example, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are preferable.

Phosphoric acid, phosphonic acid, and phosphinic acid are examples of phosphoric acid and derivatives thereof, and phosphonic acid is particularly preferable among them.

Examples of the derivative of the phosphorous oxo acid include an ester in which the hydrogen atom of the oxo acid is substituted with a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, .

Examples of phosphoric acid derivatives include phosphoric acid esters such as di-n-butyl phosphate and diphenyl phosphate.

Examples of phosphonic acid derivatives include phosphonic acid esters such as phosphonic acid dimethyl ester, phosphonic acid-di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester and phosphonic acid dibenzyl ester.

Examples of phosphinic acid derivatives include phosphinic acid esters such as phenylphosphinic acid.

The component (E) may be used alone or in combination of two or more.

The component (E) is usually used in a range of 0.01 to 5.0 parts by mass based on 100 parts by mass of the component (A).

The positive resist composition of the present invention can further contain miscible additives as desired, for example, an additive resin for improving the performance of the resist film, a surfactant for improving coatability, a dissolution inhibitor, a plasticizer, A coloring agent, a halation inhibitor, a dye, and the like may be suitably added and contained.

The positive resist composition of the present invention can be produced by dissolving the material in an organic solvent (hereinafter sometimes referred to as component (S)).

The component (S) may be any one that can dissolve each component to be used to form a homogeneous solution. Any one of known solvents for chemically amplified resists may be appropriately selected and used .

Lactones such as? -Butyrolactone; Ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone and 2-heptanone; Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; A compound having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; a monomethyl ether, monoethyl ether, Monoalkyl ethers such as monopropyl ether and monobutyl ether, and compounds having an ether bond such as monophenyl ether [among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) is preferred; Cyclic ethers such as dioxane, esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate; An anisole, an ethylbenzyl ether, a cresyl methyl ether, a diphenyl ether, a dibenzyl ether, a phenetole, a butylphenyl ether, an ethylbenzene, a diethylbenzene, a pentylbenzene, an isopropylbenzene, a toluene, a xylene, , Aromatic dimethylsulfoxide (DMSO), and the like.

These organic solvents may be used alone or in combination of two or more.

Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME) and EL are preferable.

A mixed solvent in which PGMEA and a polar solvent are mixed is also preferable. The compounding ratio (mass ratio) may be appropriately determined in consideration of the compatibility of the PGMEA and the polar solvent, and is preferably in the range of 1: 9 to 9: 1, more preferably 2: 8 to 8: 2 desirable.

More specifically, when EL is mixed as a polar solvent, the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. When PGME is blended as a polar solvent, the mass ratio of PGMEA: PGME is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2, still more preferably 3: 7 to 7 : 3.

Further, as the component (S), a mixed solvent of at least one selected from PGMEA and EL and? -Butyrolactone is also preferable. In this case, as the mixing ratio, the mass ratio of the former to the latter is preferably 70:30 to 95: 5.

The amount of the component (S) to be used is not particularly limited, but is appropriately set in accordance with the thickness of the coating film at a concentration that can be applied to a substrate or the like. In general, the solid content concentration of the resist composition is in the range of 1 to 20% by mass, preferably 2 to 15% by mass.

&Lt; Method of forming resist pattern &

The method for forming a resist pattern of the present invention includes the steps of forming a resist film on a support using the positive resist composition of the present invention, exposing the resist film, and developing the resist film to form a resist pattern .

The resist pattern forming method of the present invention can be carried out, for example, as follows.

That is, first, the resist composition is coated on a support with a spinner or the like, and then prebaked (post-apply baking (PAB)) is performed for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of 80 to 150 ° C , Exposure can be performed using a mask (mask pattern) having a predetermined pattern formed thereon, or exposure of an electron beam without a mask pattern interposed therebetween by using an exposure apparatus such as an ArF exposure apparatus, an electron beam lithography apparatus, or an EUV exposure apparatus, And then PEB (post exposure baking) is carried out for 40 to 120 seconds, preferably 60 to 90 seconds, under temperature conditions of 80 to 150 占 폚. This is then subjected to a development treatment using an alkali developing solution, for example, an aqueous solution of 0.1 to 10 mass% tetramethylammonium hydroxide (TMAH), preferably a pure water, and dried. In some cases, a baking process (post-baking) may be performed after the developing process.

In this manner, a resist pattern faithful to the mask pattern can be obtained.

The support is not particularly limited and conventionally known ones can be used. For example, a substrate for an electronic component or a wiring pattern formed on the substrate can be exemplified. More specifically, a metal substrate such as a silicon wafer, copper, chromium, iron or aluminum, or a glass substrate can be given. As the material of the wiring pattern, for example, copper, aluminum, nickel, gold and the like can be used.

The substrate may be a substrate on which an inorganic and / or organic film is formed on the above-described substrate. As the inorganic film, an inorganic anti-reflection film (inorganic BARC) can be mentioned. Examples of the organic film include an organic antireflection film (organic BARC) and an organic film such as a lower organic film in the multilayer resist method.

Here, the multilayer resist method is a method in which at least one organic film (lower organic film) and at least one resist film (upper resist film) are formed on a substrate and the resist film formed on the upper resist film is used as a mask It is said that a high aspect ratio pattern can be formed by patterning the underlying organic film. That is, according to the multilayer resist method, since the required thickness can be ensured by the lower organic film, the resist film can be made thinner and a fine pattern with a high aspect ratio can be formed.

In the multilayer resist method, a method of basically forming a two-layer structure of an upper resist film and a lower layer organic film (two-layer resist method), and a method of forming an intermediate layer (metal thin film or the like) Layer structure (a three-layer resist method).

The wavelength to be used for exposure is not particularly limited and may be selected from the group consisting of ArF excimer laser, KrF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam) Can be used. The resist composition is highly useful as KrF excimer laser, ArF excimer laser, EB or EUV, and is particularly useful for ArF excimer laser.

The exposure method of the resist film may be a conventional exposure (dry exposure) performed in air or an inert gas such as nitrogen, or may be liquid immersion lithography.

The liquid immersion exposure is an exposure method in which a space between a resist film and a lens at the lowermost position of the exposure apparatus is filled with a solvent (immersion medium) having a refractive index larger than that of air, and exposure (immersion exposure) is performed in this state.

As the immersion medium, a solvent having a refractive index that is larger than the refractive index of air and smaller than the refractive index of the exposed resist film is preferable. The refractive index of such a solvent is not particularly limited as long as it is within the above range.

Examples of the solvent having a refractive index higher than that of air and lower than the refractive index of the resist film include water, a fluorine-based inert liquid, a silicone-based solvent, and a hydrocarbon-based solvent.

Specific examples of the fluorine-based inert liquid include liquids containing fluorine-based compounds such as C ₃ HCl ₂ F ₅ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , C ₅ H ₃ F ₇ , And preferably has a boiling point of 70 to 180 ° C, more preferably 80 to 160 ° C. If the fluorine-based inert liquid has a boiling point in the above-mentioned range, it is preferable that the medium used for liquid immersion can be removed by a simple method after the end of exposure.

As the fluorine-based inert liquid, a perfluoroalkyl compound in which all the hydrogen atoms of the alkyl group are substituted with fluorine atoms is preferable. Specific examples of the perfluoroalkyl compound include a perfluoroalkyl ether compound and a perfluoroalkylamine compound.

Specific examples of the perfluoroalkyl ether compound include perfluoro (2-butyl-tetrahydrofuran) (boiling point: 102 ° C), and the perfluoroalkylamine compounds include perfluoro Butylamine (boiling point 174 DEG C).

As the immersion medium, water is preferably used from the viewpoints of cost, safety, environmental problems, versatility and the like.

The positive resist composition of the present invention is excellent in lithography properties such as an exposure margin (EL), a mask error factor (MEEF), and an in-plane uniformity of pattern dimensions (critical dimension unity (CDU)).

EL refers to the range of the exposure dose at which a resist pattern can be formed with a dimension such that the deviation from the target dimension is within a predetermined range when exposure is performed by changing the exposure dose, that is, the range of the exposure dose at which a resist pattern faithful to the mask pattern is obtained. The larger the value is, the smaller the variation amount of the pattern size accompanying the variation of the exposure amount is, and the margin of the process is improved, which is preferable.

MEEF means a mask pattern in which when a resist pattern is formed by changing the mask pattern dimension (the hole diameter in the hole pattern or the line width in the line pattern) while keeping the pitch fixed, It is one of the parameters indicating how faithfully a pattern with a different dimension can be faithfully reproduced (mask reproducibility). In the conventional resist composition, the amount of light irradiated to the exposure portion is increased or decreased by a change in the pattern dimension of the mask used for forming the resist pattern. As a result, the size of the formed resist pattern is shifted from the target dimension, When a fine pattern is formed, the shape may collapse. For example, when a hole pattern having a hole diameter of about 100 nm or less is formed, there is a fear that the roundness of the hole is lowered.

The reason that the effect obtained is not sure, the first (A1) component that has the two, the side chain -W-OSO ₂ (A1) with a structural unit (a0) having a structure of N and the structural unit (a1) component , Diffusion of the acid generated from the component (B) to the unexposed portion of the resist film in the exposed portion of the resist film is suppressed, and dissociation of the acid dissociable, dissolution inhibiting group in the component (A1) . In addition, since the sulfamoyloxy group (OSO ₂ N group), which is a polar group, is contained, the resist film has an appropriate affinity for an alkali developing solution, and both W and sulfamoyloxy groups in the constituent unit (a0) It is possible to consider that the transparency of the component (A1) is high, particularly the transparency to light of a wavelength around 193 nm is high, and thus the transparency of the formed resist film is high.

The positive resist composition of the present invention also shows the effect of forming a resist pattern in which the occurrence of defects is suppressed.

The defect refers to a general problem detected when, for example, a surface defect observation apparatus (trade name &quot; KLA &quot;) of KLA Tencor Corporation observes a resist pattern after development from directly above. This problem refers to, for example, scum after development, bubbles, dust, bridges between resist patterns, color heterogeneity, precipitates, and the like. The problem of defects becomes more important as the pattern becomes finer.

As one of the causes of the defect, it is conceivable that the surface of the resist film has a high hydrophobicity. For example, when rinsing with water after development, components such as a base resin dissolved in an alkaline developer may be re-precipitated and adhered to the surface of the resist pattern having high hydrophobicity. Therefore, it is presumed that if the hydrophilicity of the surface of the resist pattern is increased, the occurrence of defects can be suppressed. For example, when a structural unit containing a hydrophilic group such as a hydroxyl group is introduced into a base resin, hydrophilicity of the entire resist composition is increased, and the above-described defects can be reduced. However, when the proportion of the structural unit containing a hydrophilic group in the base resin is increased, the ratio of the other structural units is relatively low, so that sufficient lithographic properties can not be obtained.

On the other hand, according to the positive resist composition of the present invention, since it has a sulfamoyloxy group (OSO ₂ N group) as a polar group, hydrophilicity of the surface of the resist film to be formed is high, and defects can be reduced. Also, as described above, lithography characteristics are also good.

The hydrophobicity and hydrophilicity of the resist film are determined by the contact angle with water, for example, the static contact angle (the angle between the surface of the water droplet on the resist film in the horizontal state and the resist film surface), the dynamic contact angle (the water droplet is rolled ), A contact angle (forward angle) at an end point in front of the falling direction of the water droplet, and a contact angle (backward angle) at a backward point in the falling direction are measured Can be evaluated. For example, the higher the hydrophobicity of the resist film, the larger the static contact angle, the advancing angle and the receding angle, and the decreasing angle.

The above-mentioned various angles (dynamic contact angle (forward angle, backward angle, tilting angle, etc.) and static contact angle) were measured using DROP MASTER-700 (product name, manufactured by Kyowa Interface Science Co.), AUTO SLIDING ANGLE: SA- (Trade name, manufactured by Interface Science Co., Ltd.), and AUTO DISPENSER: AD-31 (product name, manufactured by Kyowa Interface Science Co., Ltd.).

&Lt; Polymer compound &

The polymer compound of the present invention is a polymer compound having a structural unit (a0) represented by the following general formula (a0-1) and a structural unit (a1) derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group.

The description of the polymer compound of the present invention is the same as the description of the component (A1) of the positive resist composition of the present invention.

(82)

Wherein R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms; R ² and R ³ each independently represent a hydrogen atom or an alkyl group which may contain an oxygen atom at an arbitrary position, or both form an alkylene group; W represents a cyclic alkylene group which may contain an oxygen atom at an arbitrary position]

Example

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

In the present embodiment, the unit represented by the formula (m0-1) is described as &quot; compound (m0-1) &quot;

(M1-1), (m1-1) to (m1-7), (m2-1) to (m2-9), (m3-1) to (m3-2) in the polymer synthesis example ) and (m4-1) are shown below. Of these, the compounds (m0-1), (m2-8), and (m2-9) were synthesized by Monomer Synthesis Examples 1 to 3 described later, respectively. Compound (m1-7) was synthesized in the same manner as in Synthesis Examples 1 to 2 described in JP-A-2009-223300.

Further, in the analysis by NMR, the internal standard of ¹ H-NMR and the internal standard of ¹³ C-NMR are tetramethylsilane (TMS). The internal standard for ¹⁹ F-NMR is hexafluorobenzene (with the peak of hexafluorobenzene at -160 ppm).

(83)

(84)

(85)

&Lt; EMI ID =

[Monomer Synthesis Example 1: Synthesis of compound (m0-1) (3-sulfamoyloxyadamantyl methacrylate)

A 5 L four-necked flask equipped with a thermometer, a dropping funnel and a stirrer was charged with nitrogen, and 980 g of heptane and 334 g (2.4 mol) of chlorosulfonyl isocyanate were charged from a dropping funnel. After the inner temperature was cooled to 5 캜, 110 g (2.4 mol) of formic acid was added dropwise from the dropping funnel at a rate capable of maintaining an internal temperature of 5 to 8 캜. After completion of dropwise addition, the inner temperature was raised to 20 占 폚 and stirred for 10 hours. To the reaction mixture was added a solution of 186.7 g (0.79 mol) of 3-hydroxyadamantyl methacrylate, 525 g of N-methylpyrrolidone, 2.1 g of 4-methoxyphenol and 2.1 g of phenothiazine from a dropping funnel , And dropped at a rate capable of maintaining an internal temperature of 20 占 폚 or less. After stirring at an internal temperature of 20 to 25 ° C for 3 hours, the reaction mixture was transferred to a separatory funnel and the upper layer was discarded. To the obtained lower layer were added 890 g of ethyl acetate and 700 g of water, followed by stirring and standing, followed by separation. To the aqueous layer was added 890 g of ethyl acetate and reextracted. Two portions of the ethyl acetate layer were mixed and then washed five times with 900 g of water. Followed by washing with 400 g of a 7 mass% aqueous solution of sodium hydrogencarbonate and 400 g of water. After the washing, the organic layer was concentrated under reduced pressure to 500 g, and then 630 g of toluene was added. After the inside temperature was heated to 55 캜, the temperature was cooled to 3 캜 and recrystallization operation was carried out. The resulting suspension was filtered to obtain 159.5 g (0.51 mol) of the target compound (m0-1) as crystals (Yield = 64%).

¹ H-NMR analysis results of the obtained 3-sulfamoyloxyadamantyl methacrylate are shown below.

¹ H-NMR (300MHz, solvent of dimethyl sulfoxide _{(DMSO-d 6)) :(} ppm) = 7.43 (2H, s), 5.96 (1H, s), 5.62 (1H, s), 2.48 (2H, s), 2.35 (3H, br), 2.23 (1H, s), 2.04 (6H, m), 1.84 (3H, s), 1.52 (2H, s).

[Monomer synthesis example 2: synthesis of compound (m2-8)] [

20 g (105.14 mmol) of alcohol (1), 30.23 g (157.71 mmol) of ethyldiisopropylaminocarbodiimide (EDCI) hydrochloride and 157.71 mmol of dimethylaminopyridine (DMAP) were added to a 500 ml three- 300 ml of a THF solution of 0.6 g (5 mmol) was added and 16.67 g (115.66 mmol) of the precursor 1 was added thereto under ice-cooling (0 占 폚), followed by stirring at room temperature for 12 hours.

After disappearance of the starting material was confirmed by thin layer chromatography (TLC), 50 ml of water was added to stop the reaction. The reaction solvent was concentrated under reduced pressure, and extracted three times with ethyl acetate. The obtained organic layer was washed with water, saturated sodium hydrogencarbonate and 1N-HClaq in this order. The solvent was distilled off under reduced pressure, and the obtained product was dried to obtain the desired compound (m2-8).

The analytical results of the obtained compound were as follows.

[Chemical Formula 87]

[Monomer synthesis example 3: synthesis of compound (m2-9)] [

In a three-necked flask, 50 g of precursor (2) and 37.18 g of alcohol (1) were dissolved in 500 ml of tetrahydrofuran (THF) under a nitrogen atmosphere. Then, 56.07 g of ethyldiisopropylaminocarbodiimide hydrochloride (EDCl.HCl) was added, and the mixture was cooled to 0 占 폚. Then, dimethylaminopyridine (DMAP) was added, and the mixture was allowed to react for 10 minutes. Thereafter, the reaction was allowed to proceed at room temperature for 12 hours. After completion of the reaction, 100 ml of water was added, and the mixture was concentrated under reduced pressure. The organic layer obtained by extraction with ethyl acetate was washed with water. Subsequently, the operation of washing the organic layer obtained by extraction with ethyl acetate with an aqueous solution of sodium hydrogencarbonate was repeated three times. Subsequently, the organic layer obtained by extraction with ethyl acetate was washed with water. Next, the operation of washing the organic layer obtained by extraction with ethyl acetate with an aqueous hydrochloric acid solution was repeated twice. Next, the operation of washing the organic layer obtained by extraction with ethyl acetate with water was repeated three times. Thereafter, the mixture was concentrated under reduced pressure, washed twice with heptane, and then dried to obtain 58.10 g of the desired compound (m2-9).

The analytical results of the obtained compound were as follows.

[Formula 88]

[Polymer Synthesis Example 1: Synthesis of Polymer Compound 1]

8.00 g (25.32 mmol) of the compound (m2-8) and 6.56 g (20.85 mmol) of the compound (m0-1) were added to a separable flask connected with a thermometer, a reflux tube and a nitrogen- And dissolved in methyl ethyl ketone (MEK). To this solution, 9.68 mmol of dimethyl azobisisobutyrate (V-601) as a polymerization initiator was added and dissolved. This solution was added dropwise over 3 hours to a solution of 26.92 g (102.76 mmol) of the compound (m1-3) dissolved in 26.92 g of MEK and heated to 80 占 폚 under a nitrogen atmosphere. After completion of dropwise addition, the reaction solution was heated and stirred for 2 hours, and then the reaction solution was cooled to room temperature.

The resulting reaction solution was added dropwise to a large amount of n-heptane / isopropyl alcohol mixed solvent to precipitate a polymer. The precipitated white powder was separated by filtration, washed with methanol and MEK, and dried to obtain the desired polymer compound 1 &Lt; / RTI &gt;

With respect to this polymer compound, the copolymer composition ratio (ratio (molar ratio) of each constitutional unit in the structural formula) determined by carbon 13 nuclear magnetic resonance spectrum (600 MHz ¹³ C-NMR) was l / m / n = 26.0 / 53.2 / 20.8. The mass average molecular weight (Mw) in terms of standard polystyrene determined by GPC measurement was 8,500 and the molecular weight dispersion degree (Mw / Mn) was 1.65.

(89)

[Polymer Synthesis Examples 2 to 29]

Polymeric compounds 2 to 29 were synthesized in the same manner as in Polymer Synthesis Example 1 except that the compounds shown in Tables 1 to 3 were used in a predetermined molar ratio as monomers.

The copolymer composition ratio, Mw and Mw / Mn were measured for the resulting polymer compound in the same manner as described above. The results are shown in Tables 1 to 3.

[Comparative Polymer Synthesis Examples 1 to 7]

Polymer compounds 1 'to 7' were synthesized in the same manner as in Polymer Synthesis Example 1, except that the compounds shown in Table 4 were used in a predetermined molar ratio as monomers.

The copolymer composition ratio, Mw and Mw / Mn were measured for the resulting polymer compound in the same manner as described above. The results are shown in Table 4.

&Lt; Evaluation of TMAH aqueous solution affinity of polymer compound >

[Measurement of static contact angle (CA)]

With respect to the polymeric compounds 1, 1 ', 3', 4 ', 4, 5', 5, 6 ', 6 and 7' obtained above, the affinity of the 2.38 mass% aqueous TMAH solution was evaluated by the following method.

First, these polymer compounds were dissolved in a mixed solvent of PGMEA: PGME = 6: 4 (mass ratio), respectively, to prepare a resin solution for evaluation at a concentration of 3.7 mass%. Subsequently, the resulting resin solution for evaluation was applied on an 8-inch silicon wafer using a spinner, and the resin film was dried and baked on a hot plate at 110 DEG C for 60 seconds to form a resin film having a thickness of 120 nm.

2 占 퐇 of 2.38% by mass aqueous solution of TMAH was dropped onto the surface of the resin film and the static contact angle was measured using DROP MASTER-700 (product name, manufactured by Kyowa Interface Science Co., Ltd.). This measured value was called "CA (°)". The results are shown in Table 5.

From the results in Table 5, it can be said that the polymer compounds 1, 3 to 6 relating to the present invention have low contact angles of the TMAH aqueous solution and high affinity of the alkali developing solution in comparison of the respective resins. In this respect, it is expected that the effect of suppressing the occurrence of defects in the development process can be expected also in the lithography using the positive resist composition having the polymer compound according to the present invention.

&Lt; Evaluation of positive resist composition >

[Example 1, Comparative Example 1]

Each component shown in Table 6 was mixed and dissolved to prepare a positive resist composition.

The abbreviations in Table 6 have the following meanings. The numerical value in [] is the compounding amount (parts by mass).

(A) -1: the above polymer compound 1.

(A) -1 ': the polymer compound 1'.

(B) -1: A compound represented by the following formula (B) -1 synthesized in the same manner as in Example 1 described in JP-A-2009-167156.

(B) -2: A compound represented by the following formula (B) -2.

(D) -1: tri-n-pentylamine.

(S) -1:? -Butyrolactone.

(S) -2: PGMEA / PGME = 6/4 (mass ratio) mixed solvent.

(90)

Using the obtained positive resist composition, a resist pattern was formed according to the following procedure, and the lithography characteristics were evaluated.

[Formation of resist pattern (1)]

ARC29A &quot; (trade name, manufactured by Brewers Scientific Co., Ltd.) was applied on an 8-inch silicon wafer using a spinner and baked on a hot plate at 205 DEG C for 60 seconds and dried to obtain a film having a thickness of 77 nm An organic antireflection film was formed. Then, the resist composition was applied on the antireflection film using a spinner and subjected to a prebake (PAB) treatment on a hot plate at 100 DEG C for 60 seconds to dryness to form a resist film having a thickness of 120 nm Respectively.

Next, an ArF excimer laser (193 nm) was irradiated to the resist film through a mask using an ArF exposure apparatus NSR-S302A (Nikon Corporation; NA (numerical aperture) = 0.6, 2/3 Annular) . After PEB treatment for 60 seconds at 100 占 폚, alkali development was carried out at 23 占 폚 for 30 seconds with 2.38% by mass of TMAH aqueous solution NMD-3 (trade name, manufactured by Tokyo Kyoe Kogyo Co., Ltd.) The water was rinsed with pure water for a second, and the water was dried by shaking.

As a result, a resist pattern (L / S pattern) of line-and-space (1: 1) having a line width of 130 nm and a pitch of 260 nm was formed in the resist film. The optimum exposure amount Eop (mJ / cm 2), that is, the sensitivity was obtained at this time. The results are shown in Table 7.

[EL evaluation (1)]

The exposure amount when the line of the L / S pattern is formed within the range of ± 5% (123.5 nm to 136.5 nm) of the target dimension (line width 130 nm) is determined and EL (unit:%) I got it. The results are shown in Table 7. The larger the value of EL, the smaller the amount of change in the pattern dimension due to the variation of the exposure amount.

EL (%) = (| E1 - E2 | / Eop) 100

(MJ / cm 2) when an L / S pattern having a line width of 123.5 nm is formed, E 2 is an exposure amount (mJ / cm 2) when an L / S pattern having a line width of 136.5 nm is formed, )]

[MEEF Evaluation (1)]

Using the above Eop, a mask targeting a L / S pattern having a line width of 120 nm and a pitch of 260 nm and a mask targeting a L / S pattern having a line width of 130 nm and a pitch of 260 nm were used to form an L / S pattern And the value of MEEF was obtained from the following equation. The results are shown in Table 7. The closer the MEEF value is to 1, the more the resist pattern faithful to the mask is formed.

MEEF = | CD130 - CD120 | / | MD130 - MD120 |

In the above equation, CD130 and CD120 are actual line widths (nm) of the L / S pattern formed using masks targeting line widths of 130 nm and 120 nm, respectively. MD130 and MD120 are respectively the line width (nm) targeted by the mask, and MD130 = 130 and MD120 = 120.

[Example 2, Comparative Example 2]

The components shown in Table 8 were mixed and dissolved to prepare a positive resist composition.

In Table 8, (D) -1, (S) -1 and (S) -2 are the same as above, and the other terms have the following meanings. The numerical value in [] is the compounding amount (parts by mass).

(A) -2: the above polymer compound 2.

(A) -2 ': the polymer compound 2'.

(B) -3: Component (B) to be described later A compound represented by the following formula (B) -3 synthesized in Synthesis Example 1 (the anion moiety was synthesized based on JP-A-2009-91350 ).

[Formula 91]

Using the obtained positive resist composition, a resist pattern was formed according to the following procedure, and the lithography characteristics were evaluated.

[Formation of resist pattern (2)]

ARC29 &quot; (trade name, manufactured by Brewers Scientific Co., Ltd.) was applied onto a 12-inch silicon wafer using a spinner and baked on a hot plate at 205 DEG C for 60 seconds and dried to obtain an organic An antireflection film was formed. On the antireflection film, the positive resist composition prepared as described above was applied using a spinner, PAB treatment was performed on a hot plate at 90 DEG C for 60 seconds, and the resist film was dried to form a resist film having a thickness of 100 nm .

Next, a protective film forming coating liquid &quot; TILC-035 &quot; (trade name, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was coated on the resist film using a spinner and heated at 90 캜 for 60 seconds to form a resist film having a thickness of 35 nm To form a topcoat.

Next, an ArF excimer laser (193 nm) was applied to the resist film on which the topcoat was formed with a mask via an ArF liquid immersion exposure apparatus NSR-S609B (Nikon Corporation; NA (numerical aperture) = 1.07, Annular) Respectively. Thereafter, PEB treatment was performed at 85 캜 for 60 seconds, and further alkali development was performed at 23 캜 for 30 seconds with 2.38% by mass of TMAH aqueous solution NMD-3 (trade name, manufactured by Tokyo Kasei Kogyo Co., Ltd.) And water was removed by drying.

As a result, in any of the examples, a contact hole pattern (hereinafter referred to as a CH pattern) in which holes having a hole diameter of 85 nm were arranged at equal intervals (pitch of 140 nm) was formed in the resist film. The optimum exposure amount Eop (mJ / cm 2), that is, the sensitivity was obtained at this time. The results are shown in Table 9.

[EL evaluation (2)]

An EL (unit:%) was obtained from the following formula by determining the exposure amount when the hole of the CH pattern was formed with ± 5% (80.75 nm, 89.25 nm) of the target dimension (hole diameter 85 nm). The results are shown in Table 9.

EL (%) = (| E1 '- E2' | / Eop) 100

E2 'represents the exposure (mJ / cm &lt; 2 &gt;) when a CH pattern having a hole diameter of 89.25 nm is formed, and E2' represents an exposure amount Indicates]

[MEEF Evaluation (2)]

A CH pattern was formed by using a mask targeting a CH pattern having a hole diameter of 85 nm and a pitch of 140 nm and a CH target having a hole diameter of 90 nm and a pitch of 140 nm as the target with the above Eop, The MEEF value was obtained. The results are shown in Table 9.

MEEF = | CD90 - CD85 | / | MD90 - MD85 |

In the above formulas, CD90 and CD85 are actual hole diameters (nm) of CH patterns formed by using masks targeting 90 nm and 85 nm holes, respectively. MD90 and MD85 are the hole diameters (nm) targeted by the mask, respectively, and MD90 = 90 and MD85 = 85.

[CDU evaluation]

100 hole diameters (CD) of CH patterns having a hole diameter of 85 nm formed by the Eop were measured, and three times (3s) of the standard deviation (s) was calculated as a scale representing CDU. The smaller the value of 3s, the better CDU means. The results are shown in Table 9.

[Examples 3 to 15 and Comparative Examples 3 to 4]

A positive resist composition was prepared in the same manner as in Example 2 except that the polymer compound shown in Table 10 was used in place of the polymer compound (A) -2 (Polymer Compound 2).

A resist pattern (CH pattern) was formed in the same manner as in the formation of the resist pattern (2) except that the temperatures of PAB and PEB were changed to the temperatures shown in Table 10, respectively, ), MEEF evaluation (2) and CDU evaluation. The results are shown in Table 10.

[Examples 16 to 24]

A positive resist composition was prepared in the same manner as in Example 2 except that the polymer compound shown in Table 11 was used in place of the polymer compound (A) -2 (Polymer Compound 2).

A resist pattern (CH pattern) was formed in the same manner as in the formation of the resist pattern (2) except that the temperatures of the PAB and PEB were changed to the temperatures shown in Table 11, respectively, ), MEEF evaluation (2) and CDU evaluation. The results are shown in Table 11.

As shown in the results, the positive resist composition of the present invention was excellent in lithography properties such as EL, MEEF, and CDU. Further, it was confirmed that CDU was improved when a polymer having at least two kinds of the structural units (a1) and (a2) was contained (Examples 2 and 16 to 24 for Examples 3 to 15) .

[Component (B) Synthesis Example 1 (Synthesis of (B) -3)]

35.6 g of compound (VII) (TDPS-BR) was dissolved in 360 g of pure water, to which 360 g of dichloromethane and 38.0 g of compound (VIII) were added, respectively, and the mixture was stirred at room temperature for 14 hours. Thereafter, the dichloromethane layer was separated, washed with diluted hydrochloric acid, and washed with water. The dichloromethane layer was concentrated to dryness to obtain the aimed compound (58 g) as a white solid.

This compound was analyzed by NMR to confirm its structure.

&Lt; EMI ID =

The preferred embodiments of the present invention have been described above, but the present invention is not limited to these embodiments. Additions, omissions, substitutions, and other changes may be made without departing from the scope of the present invention. The present invention is not limited by the foregoing description, but is limited only by the scope of the appended claims.

Claims (12)

1. A positive resist composition comprising a base component (A) that increases solubility in an alkali developing solution by the action of an acid, and an acid generator component (B) that generates an acid upon exposure,
(A) comprises a structural unit (a0) represented by the following general formula (a0-1) and a polymer (A1) having a structural unit (a1) derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group: Wherein the positive resist composition is a positive resist composition.

Wherein R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms; R ² and R ³ represent a hydrogen atom; W represents a cyclic alkylene group which may contain an oxygen atom at an arbitrary position] 1. A positive resist composition comprising a base component (A) that increases solubility in an alkali developing solution by the action of an acid, and an acid generator component (B) that generates an acid upon exposure,
(A) comprises a structural unit (a0) represented by the following general formula (a0-1), a structural unit (a1) derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group, and a --SO ₂ - containing cyclic group derived from an acrylate ester containing a structural unit a positive resist composition comprising the polymer compound (A1) having the ^(S a2).

Wherein R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms; R ² and R ³ each independently represent a hydrogen atom or an alkyl group which may contain an oxygen atom at an arbitrary position, or both form an alkylene group; W represents a cyclic alkylene group which may contain an oxygen atom at an arbitrary position] The method according to claim 1,
Wherein the polymer compound (A1) is at least one selected from the group consisting of a constituent unit derived from an acrylate ester containing a -SO ₂ -containing cyclic group and a constituent unit derived from an acrylate ester containing a lactone- A positive resist composition comprising one kind of the structural unit (a2). 3. The method of claim 2,
The polymeric compound (A1) is, further, a lactone-containing positive resist composition having the structural unit (a2 ^L) derived from an acrylate ester containing a cyclic group. 3. The method according to claim 1 or 2,
Wherein the polymer compound (A1) further comprises a structural unit (a3) derived from an acrylate ester containing a polar group-containing aliphatic hydrocarbon group. 3. The method according to claim 1 or 2,
Wherein the polymer compound (A1) further comprises a structural unit (a4) derived from an acrylate ester containing an aliphatic cyclic group of acid-labile nature. 3. The method according to claim 1 or 2,
Further, a positive resist composition comprising a nitrogen-containing organic compound component (D) (excluding the above-mentioned polymer compound (A1)). A process for producing a resist, comprising the steps of: forming a resist film on a support using the positive resist composition according to claim 1 or 2; exposing the resist film; and developing the resist film with alkali to form a resist pattern Pattern formation method. (A1) represented by the following general formula (a0-1), a structural unit (a1) derived from an acrylate ester containing an acid dissociable, dissolution inhibiting group, and a structural unit derived from an acrylate ester containing a -SO ₂ -containing cyclic group polymer having the structural unit (a2 ^S) is.

Wherein R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms; R ² and R ³ each independently represent a hydrogen atom or an alkyl group which may contain an oxygen atom at an arbitrary position, or both form an alkylene group; W represents a cyclic alkylene group which may contain an oxygen atom at an arbitrary position] 10. The method of claim 9,
Further, the polymer having the structural unit (a2 ^L) derived from an acrylate ester containing a lactone-containing cyclic group. 10. The method of claim 9,
Further, a polymer compound having a structural unit (a3) derived from an acrylate ester containing a polar group-containing aliphatic hydrocarbon group. 10. The method of claim 9,
Further, a polymer compound having a structural unit (a4) derived from a non-acid dissociable, acrylic acid cyclic alkyl ester.